Vinyl chloride polymer composition

ABSTRACT

The present invention provides a vinyl chloride polymer composition which comprises (i) a vinyl chloride polymer (a) and (ii) a block copolymer (b) having a polymer block (I) comprising of a block copolymer, which may be hydrogenated, of an aromatic vinyl compound polymer block and a conjugated diene polymer block, and a polymer block (II) of a polyurethane, in a specific weight ratio. The vinyl chloride polymer composition of the present invention has non-tackiness, excellent handling properties, favorable flexibility and mechanical properties, and favorable melt-adhesiveness to other materials, and shows no migration of the component serving as a plasticizer. The vinyl chloride polymer composition of the present invention can be applied for various uses such as a production of various molded articles and a production of a laminated structure with other materials.

TECHNICAL FIELD

[0001] The present invention relates to a vinyl chloride polymercomposition. The vinyl chloride polymer composition of the presentinvention has non-tackiness, excellent handling properties, favorableflexibility and mechanical properties. In addition, it has favorablemelt-adhesion to other materials, and shows no migration of thecomponent serving as a plasticizer. Therefore, the vinyl chloridepolymer composition of the present invention is effectively applied forvarious molded articles taking advantages of these characteristics.

BACKGROUND ART

[0002] A vinyl chloride resin is low-cost, suitable for general purposeand applied for various uses such as hard plates, hard mold products,water and sewerage pipes, valves and joints. Further, variousmodification methods of a vinyl chloride resin are also known.

[0003] For example, a soft polyvinyl chloride composition prepared byblending polyvinyl chloride with a liquid plasticizer such as a phthalicacid ester derivative is used in various fields, because it hasflexibility and excellent strength properties. However, such a softpolyvinyl chloride composition, which contains a liquid plasticizer, hasa problem of the reduced flexibility and the embrittlement due to themigration or the volatilization of the liquid plasticizer duringlong-term use, or during use under high temperature conditions.

[0004] Under such circumstances, in order to solve such a problem, it isproposed that polymeric plasticizers having no possibility of migrationor volatilization, such as a chlorinated polyethylene, an ethylene-vinylacetate copolymer, an ethylene-carbon monoxide-vinyl acetate copolymer,a thermoplastic polyurethane and a nitrile rubber, are blended with apolyvinyl chloride [see Japanese Patent Application Laid-open Nos. Sho59-33345 and Sho 63-68654, etc.].

[0005] Whereas, as a compound having excellent properties such as impactresistance, and excellent processability, there is proposed acomposition prepared by blending a vinyl chloride resin with an aromaticvinyl block copolymer such as a styrene-butadiene block copolymer, astyrene-isoprene block copolymer or a hydrogenated product thereof [seeJapanese Patent Application Laid-open No. Hei 5-117474]. Further, theInternational Patent Application Publication No. WO94/06859 discloses acomposition prepared by blending a specific ethylene-α-olefin copolymerwith a thermoplastic resin such as a polyolefin, a polyurethane or apolyvinyl chloride, for the purpose of improving the impact resistanceof those thermoplastic resin at low temperature. The aromatic vinylblock copolymer or a hydrogenated product thereof, or the specificethylene-α-olefin copolymer can also be considered as a kind ofpolymeric plasticizer.

[0006] Thus, it is known that various polymers are blended with a vinylchloride resin as plasticizers. However, it is important that thepolymer to be blended is selected also in consideration of theprocessability as described in the Japanese Patent Application Laid-openNo. Hei 5-117474.

DISCLOSURE OF THE INVENTION

[0007] The present invention has been made in view of thesecircumstances. It is therefore an object of the present invention tonewly provide a vinyl chloride polymer composition which is excellent inhandling properties and has excellent flexibility, and shows nomigration of the plasticizer component, by blending a vinyl chloridepolymer such as polyvinyl chloride with a polymer having a favorablecompatibility therewith.

[0008] The present inventor has found that the above-described objectcan be solved by blending a vinyl chloride polymer with a specific blockcopolymer, and made further studies. As a result, the present inventorhas completed the present invention.

[0009] Thus the present invention provides a vinyl chloride polymercomposition, which comprises: (i) a vinyl chloride polymer (a); and (ii)a block copolymer (b) having a polymer block (I) of a block copolymer,which may be hydrogenated, of an aromatic vinyl compound polymer blockand a conjugated diene polymer block, and a polymer block (II) of apolyurethane in an amount such that the weight of the vinyl chloridepolymer (a) and that of the block copolymer (b) satisfy the followingequation (1):

30/70≦Wa/Wb≦98/2  (1)

[0010] ;wherein Wa and Wb mean the weights of the vinyl chloride polymer(a) and the block copolymer (b), respectively.

[0011] Here, the block copolymer (b) is quite different from any of thepolymers to be blended into the vinyl chloride polymer in theabove-described arts.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] As the vinyl chloride polymer (a) used in the present invention,polymers having 50% by weight or more of the structural unit derivedfrom vinyl chloride are preferable. The more preferred vinyl chloridepolymer is the one having 70% by weight or more of the structural unitderived from vinyl chloride, and the still more preferred vinyl chloridepolymer is the one having 80% by weight or more of the structural unitderived from vinyl chloride.

[0013] The vinyl chloride polymer (a) can contain one or more of thestructural unit derived from a vinyl monomer other than vinyl chloride.The vinyl monomer other than vinyl chloride can include vinyl compoundshaving a cyano group such as acrylonitrile and methacrylonitrile; C1-18alkyl esters of acrylic acid or C1-18 alkyl esters of methacrylic acidsuch as methyl esters, ethyl esters, propyl esters, n-butyl esters,isobutyl esters, hexyl esters, 2-ethylhexyl esters, dodecyl esters andoctadecyl esters; esters of acrylic acid or methacrylic acid and a diolsuch as ethylene glycol, propylene glycol or butanediol; vinyl esters ofa carboxylic acid having 1 to 6 carbon atoms such as acetic acid orpropionic acid; unsaturated carboxylic acids such as acrylic acid,methacrylic acid and maleic acid; unsaturated dicarboxylic anhydridessuch as maleic anhydride; (meth)acrylamides such as acrylamide,methacrylamide and N,N-dimethylacrylamide; maleimide; N-substitutedmaleimides such as N-methylmaleimide, N-ethylmaleimide,N-phenylmaleimide and N-cyclohexylmaleimide; olefins such as ethylene,propylene and butylene; conjugated dienes such as butadiene andisoprene; aromatic vinyl compounds such as styrene, α-methylstyrene andp-methylstyrene; halogenated olefins other than vinyl chloride such asvinylidene chloride; and so on.

[0014] The vinyl chloride polymer (a) has preferably an average degreeof polymerization of 300 to 5,000. By using a vinyl chloride polymer (a)having such average degree of polymerization, a vinyl chloride polymercomposition having more improved properties such as non-tackiness,mechanical properties and processability can be obtained. The averagedegree of polymerization of the vinyl chloride polymer (a) falls betweenmore preferably 400 and 3,000, still more preferably 500 and 2,000, andthe most preferably 600 and 1,500. Here, the average degree ofpolymerization of the vinyl chloride polymer (a) referred to in thisspecification means the average degree of polymerization based on itsspecific viscosity as measured in accordance with JIS K-6721.

[0015] The block copolymer (b) is a block copolymer having a polymerblock (I) of a block copolymer, which may be hydrogenated, of anaromatic vinyl compound polymer block and a conjugated diene polymerblock and a polymer block (II) of a polyurethane.

[0016] In the block copolymer (b), the bonding form of the polymer block(I) and the polymer block (II) may be linear, branched, radial or mixedtype thereof. Preferably, the polymer block (I) and the polymer block(II) are bonded in linear form.

[0017] The block copolymer (b) may have various structures such as α-β,α-β-α and β-α-β, wherein a means the polymer block (I) and β means thepolymer block (II). The di-block structure of α-β is preferred. By usingthe block copolymer (b) having adi-blockstructure, a vinyl chloridepolymer composition having more excellent properties such asnon-tackiness, flexibility and processability can be obtained.

[0018] When the block copolymer (b) has two or more of the polymerblocks (I), each polymer block (I) may be the same or different. On theother hand, when the block copolymer (b) has two or more of the polymerblocks (II), each polymer block (II) may be the same or different. Forexample, the two polymer blocks (I) in the tri-block copolymer havingthe structure of α-β-α, or the two polymer blocks (II) in the tri-blockcopolymer having the structure of β-α-β may be the same or different inthe species or the bonding forms of the structural unit, their numberaverage molecular weight, and so on.

[0019] In the block copolymer (b), the weight ratio of the polymer block(I) based on the polymerblock (II) falls between preferably 5/95 and95/5, more preferably 10/90 and 90/10, still more preferably 20/80 and80/20, and the most preferably 30/70 and 70/30.

[0020] The aromatic vinyl compound which constitutes the aromatic vinylcompound polymer block in the polymer block (I) can include, forexample, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,2,4,6-trimethylstyrene, 4-propylstyrene, t-butylstyrene,4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene,4-(phenylbutyl)styrene, 1-vinylnaphthalen, vinylanthracene, indene,acetonaphthylene, monofluorostyrene, difluorostyrene, monochlorostyreneand methoxystyrene. The aromatic vinyl compound polymer block may have astructural unit comprising only one aromatic vinyl compound, or may havea structural unit comprising two or more of the aromatic vinylcompounds. Among them, it is preferred that the aromatic vinyl compoundpolymer block mainly comprises structural units derived from styreneand/or α-methylstyrene.

[0021] The aromatic vinyl compound polymer block can optionally have aslight amount of structural units comprising other copolymerizablemonomers in addition to the structural units comprising aromatic vinylcompounds. The ratio of the structural units comprising othercopolymerizable monomers in this case is preferably 30% by weight orless, and more preferably 10% by weight or less, based on the weight ofthe aromatic vinyl compound polymer block. The other copolymerizablemonomers in this case can include, for example, 1-butene, pentene,hexene, butadiene, 2-methyl-1,3-butadiene [namely, isoprene] and methylvinyl ether.

[0022] The conjugated diene which constitutes the conjugated dienepolymer block in the polymer block (I) can include, for example,1,3-butadiene, 2-methyl-1,3-butadiene [namely, isoprene],2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and 1,3-hexadiene. Theconjugated diene polymer block may have a structural unit comprisingonly one conjugated diene, or may have a structural unit comprising twoor more of the conjugated dienes. When the conjugated diene polymerblock have a structural unit derived from two or more of the conjugateddienes, their bonding forms may be a random, tapered, partially blockform, or combination of two or more of the forms.

[0023] In the polymer block (I), the conjugated diene polymer block maybe hydrogenated partially or entirely. In this case, the hydrogenationratio of the conjugated diene polymer block is in the range ofpreferably 50 mol % or more, more preferably 60 mol % or more, and stillmore preferably 80 mol % or more, from the viewpoint of the heatresistance, the weatherability and the light-resistance.

[0024] From the viewpoint of the flexibility, mechanical properties andprocessability of the resulting vinyl chloride polymer composition, theconjugated diene polymer block in the polymer block (I) is preferably atleast one of the polymer block selected from the group consisting of apolyisoprene which may be hydrogenated, a polybutadiene which may behydrogenated and a copolymer of isoprene and butadiene which may behydrogenated.

[0025] In the polymer block (I), the bonding form of the aromatic vinylcompound polymer block and the conjugated diene polymer block may belinear, branched, radial or mixed type thereof. Preferably, they arebonded in linear form.

[0026] The polymer block (I) may have various structures such as(X—Y)_(m)—X, (X—Y)_(n) and Y—(X—Y)_(p), wherein X means the aromaticvinyl compound polymer block; Y means the conjugated diene polymerblock; and “m”, “n” and “p” mean an integer of one or more,respectively. Among them, the polymer block (I) has preferably astructure in which two or more of the aromatic vinyl compound polymerblocks [X] and one or more of the conjugated diene polymer blocks [Y]are bonded in linear form, and has more preferably the tri-blockstructure of X—Y—X, because a vinyl chloride polymer composition havingexcellent properties such as non-tackiness, flexibility, mechanicalproperties and processability can be obtained.

[0027] When the polymer block (I) has two or more of the aromatic vinylcompound polymer blocks [X], each polymer block [X] may be the same ordifferent. On the other hand, when the polymer block (I) has two or moreof the conjugated diene polymer blocks [Y], each polymer block [Y] maybe the same or different. For example, the two polymer blocks [X] in thetri-block structure of X—Y—X, or the two polymer blocks [Y] in thetri-block structure of Y—X—Y may be the same or different in the speciesor the bonding forms of the aromatic vinyl compound or the conjugateddiene, their number average molecular weights, and so on.

[0028] In the polymer block (I), the content of the structural unitderived from the aromatic vinyl compound is preferably from 5 to 90% byweight based on the total structural unit of the polymer block (I). Byusing the block copolymer (b) having a polymer block (I) in which thecontent of the structural unit derived from the aromatic vinyl compoundfalls within the above-described range, a vinyl chloride polymercomposition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.The polymer block (I) contains the structural unit derived from thearomatic vinyl compound in the range of more preferably 10 to 90% byweight, and still more preferably 20 to 80% by weight, based on thetotal structural unit thereof.

[0029] In addition, in the polymer block (I), the number averagemolecular weight of the aromatic vinyl compound polymer block and thatof the conjugated diene polymer block are not particularly limited, butthe number average molecular weight of the aromatic vinyl compoundpolymer block preferably ranges from 2,500 to 75,000, and the numberaverage molecular weight of the conjugated diene polymer blockpreferably ranges from 10,000 to 150,000, before hydrogenation. By usingthe block copolymer (b) having a polymer block (I) in which the numberaverage molecular weight of the aromatic vinyl compound polymer block orthat of the conjugated diene block falls within the above-describedrange, a vinyl chloride polymer composition having more improvedproperties such as non-tackiness, flexibility, mechanical properties andprocessability can be obtained.

[0030] The number average molecular weight of the polymer block (I) ispreferably in the range of 15,000 to 300,000 before hydrogenation. Byusing the block copolymer (b) having a polymer block (I) in which thenumber average molecular weight falls within the above-described range,a vinyl chloride polymer composition having excellent properties such asnon-tackiness, flexibility, mechanical properties and processability canbe obtained. The polymer block (I) has, more preferably, the numberaverage molecular weight of 20,000 to 100,000.

[0031] The polymer block (II) of the block copolymer (b) is a polymerblock of a polyurethane which is made of a high polymer polyol, a chainextender and an organic diisocyanate.

[0032] The high polymer polyol which constitutes the polymer block (II)can include, for example, polyester polyols, polyether polyols,polycarbonate polyols, polyester-polycarbonate polyols, polyolefinpolyols, conjugated diene polymer based polyols, castor oil basedpolyols, silicone based polyols and vinyl polymer based polyols. One ormore of these high polymer polyols can be used. Among them, thepreferred high polymer polyol is at least one of the high polymerpolyols selected from the group consisting of polyester polyols,polyether polyols and polyolefin polyols. The more preferred highpolymer polyol is polyester polyols and/or polyether polyols.

[0033] The polyester polyols can be prepared, for example, by subjectinga polyol component and a polycarboxylic acid component to theesterification reaction or the ester exchange reaction, or by subjectinga lactone to a ring-opening polymerization under the presence of apolyol component.

[0034] The polyol components used for the preparation of the polyesterpolyols can include ones conventionally used for the preparation of anester, for example, aliphatic diols having 2 to 15 carbon atoms such asethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, 1,3-propanediol, 2-methyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol,2-methyl-1,4-butanediol, neopentyl glycol, 1,5-pentanediol,3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol,1,8-octanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol,1,9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9-nonanediol and1,10-decanediol; cycloaliphatic diols such as 1,4-cyclohexanediol,cyclohexanedimethanol and cyclooctanedimethanol; aromatic diols such as1,4-bis (β-hydroxyethoxy)benzene; and polyhydric alcohols having notless than three hydroxyl groups such as trimethylolpropane,trimethylolethane, glycerin, 1,2,6-hexanetriol, pentaerythritol anddiglycerol. One or more of these compounds can be used as a polyolcomponent for the preparation of the polyester polyol.

[0035] Among them, for the preparation of the polyester polyol, thepreferred polyol component is an aliphatic diol having 5 to 12 carbonatoms and a methyl group as a side chain such as2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol,2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol,2-methyl-1,9-nonanediol or 2,8-dimethyl-1,9-nonanediol. Especially, suchan aliphatic diol having 5 to 12 carbon atoms and a methyl group as aside chain is used in the range of preferably 30 mol % or more, morepreferably 50 mol % or more, based on the total polyol component usedfor the preparation of the polyester polyol.

[0036] The polycarboxylic acid components used for the preparation -ofthe polyester polyols can include ones conventionally used for thepreparation of an ester, for example, aliphatic dicarboxylic acidshaving 4 to 12 carbon atoms such as succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid,3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedicarboxylicacid, 3,8-dimethyldecanedicarboxylic acid and3,7-dimethyldecanedicarboxylic acid; cycloaliphatic dicarboxylic acidssuch as cyclohexanedicarboxylic acid, dimer acid and hydrogenatedproduct of dimer acid; aromatic dicarboxylic acids such as terephthalicacid, isophthalic acid, orthophthalic acid and naphthalenedicarboxylicacid; polycarboxylic acids such as trimellitic acid and pyromelliticacid; and derivatives thereof which can form esters, such as carboxylicacid esters and acid anhydrides. One or more of these compounds can beused as the polycarboxylic acid component. Among them, the preferredpolycarboxylic acid component is an aliphatic dicarboxylic acid having 2to 6 carbon atoms, and the more preferred polycarboxylic acid componentis at least one compound selected from the group consisting of adipicacid, azelaic acid and sebacic acid.

[0037] The lactones used for the preparation of the polyesterpolyolscaninclude, for example, ε-caprolactone andβ-methyl-δ-valerolactone.

[0038] The polyetherpolyols can include, for example, ones prepared bythe ring-opening polymerization of a cyclic ether such as a polyethyleneglycol, a polypropylene glycol, a polytetramethylene ether glycol or apoly(methyltetramethylene ether) glycol. One or more of these polyetherpolyols can be used. Among them, the preferred polyether polyol is apolytetramethylene ether glycol and/or a poly(methyltetramethyleneether) glycol.

[0039] The polycarbonate polyols can include, for example, thoseobtained by the reaction of a polyol component and a carbonate compoundsuch as a dialkyl carbonate, an alkylene carbonate or a diarylcarbonate.

[0040] The polyol component, which constitutes the polycarbonatepolyols, can include ones exemplified above as a polyol componentconstituting the polyester polyols. The dialkyl carbonate can include,for example, dimethyl carbonate and diethylcarbonate. Examples of thealkylene carbonate can include ethylene carbonate; and examples of thediaryl carbonates can include diphenyl carbonate.

[0041] The polyester polycarbonate polyols can include, for example,those obtained by the reaction of a polyol component, a polycarboxylicacid component and a carbonate compound; those obtained by the reactionof a carbonate compound and a previously prepared polyester polyol andpolycarbonate polyol, and those obtained by the reaction of a previouslyprepared polyester polyol and polycarbonate polyol, a polyol componentand a polycarboxylic acid component.

[0042] The conjugated diene polymer based polyols, or the polyolefinpolyols can include a polyisoprene polyol, a polybutadiene polyol, apoly(butadiene/isoprene) polyol, a poly(butadiene/acrylonitrile) polyol,a poly(butadiene/styrene) polyol, and a hydrogenated product thereof,prepared by polymerizing a conjugated diene such as butadiene orisoprene, or a conjugated diene and another monomer, by a livingpolymerization method, or the like in the presence of a polymerizationinitiator, followed by a reaction with an epoxy compound. One or more ofthese conjugated diene polymer based polyols, or the polyolefin polyolscan be used.

[0043] The number average molecular weight of the high polymer polyolpreferably falls within the range of 500 to 10,000. By using the blockcopolymer (b) having a polymer block (II) made of the high polymerpolyol with such a number average molecular weight, a vinyl chloridepolymer composition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.The number average molecular weight of the high polymer polyol is in therange of more preferably 700 to 8,000, and still more preferably 800 to5,000. Here, the number average molecular weight of the high polymerpolyol referred to in this specification means the number averagemolecular weight based on its hydroxyl value as measured in accordancewith JIS K-1577.

[0044] The chain extender which constitutes the polymer block (II) caninclude ones conventionally used for the preparation of a polyurethane.Preferred chain extender is a compound having a molecular weight of notmore than 400 and having two or more active hydrogen atoms capable ofreacting with isocyanate group.

[0045] The chain extender can include, for example, diols such asethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, neopentylglycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol,2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol,2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol,2,8-dimethyl-1,9-nonanediol,1,4-bis(β-hydroxyethoxy)benzene,1,4-cyclohexanediol,bis(β-hydroxyethyl)terephthalate, xylylene glycol,1,4-cyclohexanedimethanol, 1,4- or 1,5-cyclooctanedimethanol and 3(or4),8(or 9)-dihydroxymethyltricyclo[5.2.1.0^(2,6)]decane; diamines suchas hydrazine, ethylenediamine, propylenediamine, xylylenediamine,isophorone diamine, piperazine, piperazine derivatives,phenylenediamine, toluylenediamine, adipic acid dihydrazide andisophthalic acid dihydrazide; aminoalcohols such as aminoethyl alcoholand aminopropyl alcohol; and so on. One or more of these chain extenderscan be used. Among them, the preferred chain extender is an aliphaticdiol having 2 to 12 carbon atoms, and the more preferred chain extenderis 1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol or1,9-nonanediol.

[0046] The organic diisocyanate which constitute the polymer block (II)can include ones conventionally used for the preparation of apolyurethane. Examples of the organic diisocyanate include aromaticdiisocyanates such as 4,4′-diphenylmethane diisocyanate, tolylenediisocyanate, phenylene diisocyanate, xylylene diisocyanate,1,5-naphthylene diisocyanate and 3,3′-dichloro-4,4′-diphenylmethanediisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylenediisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate) and hydrogenated xylylene diisocyanate; and so on. One ormore of these organic diisocyanates can be used. Among them, thepreferred organic diisocyanate is 4,4′-diphenylmethane diisocyanate.

[0047] The amount of the high polymer polyol, the chain extender and theorganic diisocyanate which constitute the polymer block (II) ispreferably adjusted such that the content of nitrogen derived from theorganic diisocyanate is in the range of 1 to 6.5% by weight based on thetotal weight of the high polymer polyol, the chain extender and theorganic diisocyanate. By using the block copolymer (b) having a polymerblock (II) in which the content of nitrogen derived from the organicdiisocyanate is set within the above-described range, a vinyl chloridepolymer composition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.In the polymer block (II), the content of the nitrogen derived from theorganic diisocyanate falls more preferably between 1 and 6% by weight,still more preferably between 1.3 and 5.5% by weight, and the mostpreferably between 1.6 and 5% by weight, based on the total weight ofthe high polymer polyol, the chain extender and the organicdiisocyanate.

[0048] The number average molecular weight of the polymer block (II)falls preferably between 200 and 300,000. By using the block copolymer(b) having a polymer block (II) with such a number average molecularweight, a vinyl chloride polymer composition having excellent propertiessuch as non-tackiness, flexibility, mechanical properties andprocessability can be obtained. The number average molecular weight ofthe polymer block (II) is in the range of more preferably 500 to150,000, and still more preferably 1,000 and 100,000.

[0049] The hardness of the polymer block (II) falls preferably between30 and 99, expressed in the JIS A hardness of the polyurethanecorresponding to the polymer block (II). By using the block copolymer(b) having a polymer block (II) with such a hardness, a vinyl chloridepolymer composition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.The JIS A hardness of the polyurethane corresponding to the polymerblock (II) is more preferably between 45 and 97, and still morepreferably between 60 and 95.

[0050] The block copolymer (b) can be obtained, for example, byeffecting a polyurethane forming reaction under the presence of a blockcopolymer, which may be referred to as “functionality. block copolymer”hereinafter, having a structure corresponding to the polymer block (I)and a functional group reactive with a component of the polymer block(II). That is, the block copolymer (b) can be obtained by forming thepolymer block (II) of a polyurethane on the polymer chain of a blockcopolymer, which may be hydrogenated, having an aromatic vinyl compoundpolymer block and an conjugated diene polymer block, and having afunctional group reactive with a component such as an organicdiisocyanate, a chain extender or a high polymer polyol. In addition theblock copolymer (b) can also be obtained by subjecting a functionalityblock copolymer and a polyurethane having a structure corresponding tothe polymer block (II).

[0051] Examples of the functional group which is contained in thefunctionality block copolymer and which is reactive with a component ofthe polymer block (II) can include, for example, ones reactive with ahigh polymer polyol and/or a chain extender, such as carboxyl group,acid anhydride group, thiocarboxyl group, isocyanate group, and so on;and ones reactive with an organic diisocyanate, such as hydroxyl group,amino group, mercapto group, carboxyl group, acid anhydride group,thiocarboxyl group, isocyanate group, and so on. The functionality blockcopolymer can contain one or more of these functional groups.

[0052] The functionality block copolymer has preferably a functionalgroup reactive with an organic diisocyanate. The more preferredfunctional group is hydroxyl group, because a homogeneous polyurethaneforming reaction can be conducted upon the preparation of the blockcopolymer (b).

[0053] The functional group reactive with a component of the polymerblock (II) can locate preferably on a terminal of the functionalityblock copolymer. When a functionality block copolymer having such afunctional group on a terminal of the molecule is used, the functionalgroup can participate in the extension of main chain structure bypolyurethane forming reaction upon the preparation of the blockcopolymer (b). By using the block copolymer (b) thus obtained, a vinylchloride polymer composition having excellent properties such asnon-tackiness, flexibility, mechanical properties and processability canbe obtained with reliability.

[0054] The average number of the functional group reactive with acomponent of the polymer block (II) is preferably not less than 0.6,more preferably not less than 0.7, and still more preferably between 0.7and 1 per a molecule of the functionality block copolymer.

[0055] The functionality block copolymer can be prepared by an ionicpolymerization such as an anionic polymerization or a cationicpolymerization; a single site polymerization, a radical polymerizationor the like. For example, the functionality block copolymer can beprepared by the procedures, in which an anionic polymerization isemployed, comprising successively polymerizing an aromatic vinylcompound and a conjugated diene in an inert organic solvent such asn-hexane or cyclohexane using an alkyl lithium compound as apolymerization initiator, adding a compound having an oxirane skeletonsuch as ethylene oxide, propylene oxide or styrene oxide; or a lactonesuch as ε-caprolactone, β-propiolactone, dimethylpropiolactone[pivalolactone] or methylvalerolactone when the desired molecularstructure and the desired molecular weight are obtained, and then addingan active hydrogen-containing compound such as alcohols, carboxylicacids or water to terminate the polymerization. Then the obtainedfunctionality block copolymer is preferably hydrogenated in an inertorganic solvent such as n-hexane or cyclohexane under the presence of ahydrogenation catalyst such as a Ziegler catalyst consisting analkylaluminum compound and cobalt or nickel at a reaction temperature of20 to 150° C. and at a hydrogen pressure of 1 to 150 kg/cm². Inaddition, the functionality block copolymer, before or afterhydrogenation, may be optionally modified with maleic anhydride, andsoon. The functionality block copolymer and/or the hydrogenated productthereof may contain, depending on the preparation method thereof, ablock copolymer having an aromaticvinyl compound polymer block, aconjugated diene polymer block and no functional group.

[0056] As the functionality block copolymer, commercially available onescan be used.

[0057] The number average molecular weight of the functionality blockcopolymer is in the range of preferably 15,000 to 300,000, and morepreferably 20,000 to 100,000. Here, the number average molecular weightof the functionality block copolymer is a value obtained by gelpermeation chromatography [GPC], based on the standard polystyrenecalibration curve.

[0058] The MFR [melt flow rate] of the functionality block copolymer,when measured at 230° C. under the load of 2.16 kg, falls preferablybetween 0.01 and 100 g/10 minutes. By using a functionality blockcopolymer having such an MFR value, a thermoplastic polymer compositionhaving excellent properties such as non-tackiness, processability formelt molding and melt-adhesiveness can be obtained. The MFR [melt flowrate] of the functionality block copolymer, when measured at 230° C.under the load of 2.16 kg, falls more preferably between 0.05 and 80g/10 minutes. Here, the MFR value of the functionality block copolymeris measured in according with ASTM D-1238.

[0059] The polymer block (II) or a polyurethane corresponding to thepolymer block (II) can be formed with the above-described high polymerpolyol, the chain extender and the organic diisocyanate by aconventional polyurethane forming reaction.

[0060] In the formation of the polymer block (II) or a polyurethanecorresponding to the polymer block (II), each component is employedpreferably in amounts such that the isocyanate group of the organicdiisocyanate is present by a ratio of 0.9 to 1.3 moles per 1 mole of thetotal active hydrogen atoms of the high polymer polyol and the chainextender. By using a block copolymer having the polymer block (II)prepared by a high polymer, a chain extender and an organic diisocyanatewith the above-described ratio, a vinyl chloride polymer compositionhaving more excellent properties such as non-tackiness, flexibility,mechanical properties and processability can be obtained.

[0061] Also, in the formation of the polymer block (II) and apolyurethane corresponding to the polymer block (II), it is preferableto use each component in amounts such that the content of nitrogenderived from the organic diisocyanate is in the range of 1 to 6.5% byweight based on the total weight of the high polymer polyol, the chainextender and the organic diisocyanate. By using a block copolymer (b)having the polymer block (II) formed of a high polymer polyol, a chainextender and an organic diisocyanate in the above-described ratio, avinyl chloride polymer composition having excellent properties such asnon-tackiness, flexibility, mechanical properties and processability canbe obtained. The each component is used in amounts such that the contentof nitrogen derived from the organic diisocyanate falls more preferablybetween 1 and 6% by weight, still more preferably between 1.3 and 5.5%by weight, and the most preferably between 1.6 and 5% by weight, basedon the total weight of the high polymer polyol, the chain extender andthe organic diisocyanate.

[0062] The block copolymer (b) can be easily and preferably prepared by(A) the reaction of a functionality block copolymer, a high polymerpolyol, a chain extender and an organic diisocyanate, or (B) thereaction of a functionality block copolymer and a reaction product of ahigh polymer polyol, a chain extender and an organic diisocyanate.

[0063] With respect to the reaction (B), the reaction product caninclude a reaction mixture of a high polymer polyol, a chain extenderand an organic diisocyanate, which may be further subjected to work upwith the conventional process. Also, commercially availablepolyurethanes may be used as the reaction product so long as they areprepared from a high polymer polyol, a chain extender and an organicdiisocyanate.

[0064] The reaction product of a high polymer polyol, a chain extenderand an organic diisocyanate can contain, in addition to polyurethaneproduced therefrom, the unreacted high polymer polyol, the unreactedchain extender and the unreacted organic diisocyanate according to theamounts of the reactants, degree of conversion, other reactionconditions, and so on. In this case, the reaction between afunctionality block copolymer and a polyurethane produced from a highpolymer polyol, a chain extender and an organic diisocyanate, and thereaction between a functionality block copolymer, a high polymer polyol,a chain extender and an organic diisocyanate proceed simultaneously.

[0065] When the block copolymer (b) is produced by the reaction (A), theweight ratio of a functionality block copolymer based on the sum of ahigh polymer polyol, a chain extender and an organic diisocyanate ([theweight of a functionality block copolymer]:[the total weight of a highpolymer polyol, a chain extender and an organic diisocyanate]) is in therange of preferably 5:95 to 95:5, more preferably 10:90 to 90:10, stillmore preferably 20:80 to 80:20, and the most preferably 30:70 to 70:30.

[0066] Also, when the block copolymer (b) is produced by the reaction(B), the weight ratio of a functionality block copolymer based on areaction product of a high polymer polyol, a chain extender and anorganic diisocyanate ([the weight of a functionality blockcopolymer]:[the weight of a reaction product of a high polymer polyol, achain extender and an organic diisocyanate]) is in the range ofpreferably 5:95 to 95:5, more preferably 10:90 to 90:10, still morepreferably 20:80 to 80:20, and the most preferably 30:70 to 70:30.

[0067] Upon the preparation of the block copolymer (b), a catalyst forpolyurethane forming reaction can be used. Such catalyst forpolyurethane forming reaction include organic tin compounds such asdibutyltin diacetate, dibutyltin dilaurate and dibutyltinbis(3-ethoxybutyl 3-mercaptopropionate); titanic acid; organic titaniumcompounds such as tetraisopropyl titanate, tetra-n-butyltitanate,polyhydroxytitanium stearate and titanium acetylacetonate; tertiaryamines such as triethylene diamine, N-methylmorpholine,N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylhexamethylenediamine, triethylamine and N,N-dimethylaminoethanol; and so on.

[0068] The amount of the catalyst for polyurethane forming reactionfalls preferably between 0.1 ppm and 0.2% by weight, more preferablybetween 0.5 ppm and 0.02% by weight, and still more preferably between 1ppm and 0.01% by weight, based on the total weight of the functionalityblock copolymer, the high polymer polyol, the chain extender and theorganic diisocyanate, or based on the total weight of the functionalityblock copolymer and the reaction product of the high polymer polyol, thechain extender and the organic diisocyanate.

[0069] Upon the preparation of the block copolymer (b), the catalyst forpolyurethane forming reaction can be mixed with one or more of thefunctionality block copolymer, the high polymer polyol, the chainextender, the organic diisocyanate and the reaction product of the highpolymer polyol, the chain extender and the organic diisocyanate. In themore preferred embodiments, the catalyst for polyurethane formingreaction is mixed with the high polymer polyol.

[0070] When the block copolymer (b) is produced in the presence of acatalyst for polyurethane forming reaction, it is desirable to add adeactivator of the catalyst for polyurethane forming reaction to theobtained block copolymer (b). Examples of the deactivator can includephosphorus compounds such as lauryl phosphate, oleyl phosphate, stearylphosphate, dilauryl phosphate, dioleyl phosphate, distearyl phosphate,tris(2-ethylhexyl) phosphate, bis(octadecyl) pentaerythritoldiphosphate, diethyl phenylphosphonate and diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate; phenolic compounds such as2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2-hydroxy-4-benzyloxybenzophenone,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole and4,4′-dioctyl-2,2′-biphenol. The preferred deactivator is a phosphoruscompound.

[0071] The amount of the deactivator of the catalyst for polyurethaneforming reaction falls preferably between 1 ppm and 2% by weight, morepreferably between 5 ppm and 0.2% by weight, and still more preferablybetween 10 ppm and 0.1% by weight, based on the total weight of thefunctionality block copolymer, the high polymer polyol, the chainextender and the organic diisocyanate, or based on the total weight ofthe functionality block copolymer and the reaction product of the highpolymer polyol, the chain extender and the organic diisocyanate.

[0072] The block copolymer (b) can be prepared according to theconventional urethane forming techniques. The block copolymer (b) can beprepared by either “prepolymer process” or “one-shot process”.

[0073] The block copolymer (b) is preferably prepared substantiallywithout the presence of any solvent. The block copolymer (b) ispreferably prepared by melt kneading with a machine such as asingle-screw extruder, a twin-screw extruder, a kneading machine and aBanbury mixer. The conditions for melt kneading are properly determinedon account of the species of the raw material or the kind of the machineemployed. The melt kneading is, in general, conducted at a temperatureof 180 to 260° C. for 1 to 15 minutes.

[0074] Specific examples of the reaction used for forming polyurethaneinclude the following procedures [1] to [6].

[0075] [1] A functionality block copolymer, a high polymer polyol and achain extender are mixed, for example, while heating at the temperatureof 40 to 100° C. An organic diisocyanate is added to the resultingmixture in amounts such that the molar ratio of the active hydrogenatoms based on the isocyanate groups falls preferably between 0.9 and1.3, followed by stirring for a short time. Then, the resulting mixtureis heated, for example, at the temperature of 80 to 200° C.

[0076] [2] A high polymer polyol, a chain extender and an organicdiisocyanate are continuously fed into an extruder such as a multi-screwextruder and heated, for example, at the temperature of 90 to 260° C. Afunctionality block copolymer is continuously fed into the heatedmixture at a rate such that the molar ratio of the active hydrogen atomsbased on the isocyanate groups falls preferably between 0.9 and 1.3, andcontinuously melt-polymerized at the temperature of, for example, 180 to260° C.

[0077] [3] A functionality block copolymer, a high polymer polyol, achain extender and an organic diisocyanate are continuously fed into anextruder such as a multi-screw extruder at a rate such that the molarratio of the active hydrogen atoms based on the isocyanate groups fallspreferably between 0.9 and 1.3, and continuously melt-polymerized at thetemperature of, for example, 180 to 260° C.

[0078] [4] A high polymer polyol, a chain extender and an organicdiisocyanate are continuously fed into an extruder such as a multi-screwextruder and heated, for example, at the temperature of 90 to 260° C. toeffect the polyurethane formation. A functionality block copolymer iscontinuously added to the polyurethane and continuously melt-polymerizedat the temperature of, for example, 180 to 260° C.

[0079] [5] A functionality block copolymer and a polyurethane, which maybe commercially available, are continuously fed into an extruder such asa multi-screw extruder and reacted at the temperature of, for example,180 to 260° C.

[0080] [6] A functionality block copolymer, a high polymer polyol, achain extender and an organic diisocyanate are added to an organicsolvent in amounts such that the molar ratio of the active hydrogenatoms based on the isocyanate groups falls preferably between 0.9 and1.3, to effect the polyurethane formation.

[0081] The polymer composition, which may be referred to as “blockcopolymer composition” hereinafter, obtained by the reaction of thefunctionality block copolymer, the high polymer polyol, the chainextender and the organic diisocyanate, or by the reaction of thefunctionality block copolymer and the reaction product of the highpolymer polyol, the chain extender and the organic diisocyanate,according to the above-described methods, can contain the unreacted highpolymer polyol, the unreacted chain extender or the unreacted organicdiisocyanate other than the block copolymer (b). The amounts of thesecompounds are varied according to the reaction conditions such as aratio of the reactants and reaction temperature.

[0082] The block copolymer (b) thus prepared may contain a polyurethaneformed by the high polymer polyol, the chain extender and the organicdiisocyanate. Also, the block copolymer (b) may contain a blockcopolymer, which may be hydrogenated, having an aromatic vinyl compoundpolymer block and a conjugated diene polymer block, and having afunctional group on a terminal of the molecule. In addition, the blockcopolymer (b) can contain a block copolymer having an aromatic vinylcompound polymer block, a conjugated diene polymer block and nofunctional group.

[0083] The block copolymer (b) can be obtained, for example, by theprocedures of (i) subjecting the block copolymer composition, which maybe optionally pelletized and pulverized into appropriate size, to thetreatment with a good solvent for polyurethane such as dimethylformamidein order to remove polyurethane unreacted with the functionality blockcopolymer, and the treatment with a good solvent for functionality blockcopolymer such as cyclohexane in order to remove the unreactedfunctionality block copolymer and a block copolymer corresponding to thepolymer block (I), successively, and (ii) drying the remaining solidmaterial.

[0084] In the present invention, the block copolymer composition can beemployed, as it is, for the preparation of the vinyl chloride polymercomposition as long as it does not depart from the scope of theinvention.

[0085] The vinyl chloride composition of the present invention comprisesthe vinyl chloride polymer (a) and the block copolymer (b) at a weightratio to meet the following equation (1).

30/70≦Wa/Wb≦98/2  (1)

[0086] ; wherein Wa means the weight of the vinyl chloride polymer (a)and Wb means the weight of the block copolymer (b).

[0087] When the amount of the vinyl chloride polymer (a) is less thanthe above-described range, the properties of the vinyl chloride polymercomposition such as non-tackiness, mechanical properties andprocessability are reduced. On the other hand, when the amount of thevinyl chloride polymer (a) is more than the above-described range, it isdifficult to produce a vinyl chloride polymer composition having goodflexibility. In addition, in such a case, the processability of thevinyl chloride polymer composition is reduced.

[0088] The weight ratio [Wa/Wb] of the vinyl chloride polymer (a) andthe block copolymer (b) is in the range of preferably 35/65 to 90/10,and more preferably 40/60 to 85/15.

[0089] The vinyl chloride polymer composition of the present inventioncan contain a thermoplastic polyurethane (c). As the thermoplasticpolyurethane (c), there can be used those prepared from the reaction ofthe above-describe high polymer polyol, the chain extender and theorganic diisocyanate, which is not limited to the polyurethane producedupon the preparation of the block copolymer (b). The thermoplasticpolyurethane (c) has preferably similar profiles of the polymer block(II) in the block copolymer (b).

[0090] With respect to the thermoplastic polyurethane (c), the contentof nitrogen derived from the organic diisocyanate falls preferablybetween 1 and 6.5% by weight, more preferably between 1 and 6% byweight, still more preferably 1.3 and 5.5% by weight, and the mostpreferably between 1.6 and 5% by weight, based on the total weight ofthe high polymer polyol, the chain extender and the organicdiisocyanate.

[0091] The number average molecular weight of the thermoplasticpolyurethane (c) falls preferably between 200 and 300,000, morepreferably between 500 and 150,000, and still more preferably between1,000 and 100,000. In addition, the JIS A hardness of the thermoplasticpolyurethane (c) falls preferably between 30 and 99, more preferablybetween 45 and 97, and still more preferably between 60 and 95.

[0092] The amount of the thermoplastic polyurethane (c) is preferablynot more than 1000 parts by weight, more preferably in the range of 0 to500 parts by weight, and still more preferably in the range of 0 to 300parts by weight, based on 100 parts by weight of the block copolymer(b).

[0093] The vinyl chloride polymer composition of the present inventioncan contain a block copolymer (d), which may be hydrogenated, having anaromatic vinyl compound polymer block and a conjugated diene polymerblock, which may be referred to as “aromatic vinyl compound blockcopolymer (d)” hereinafter. Such an aromatic vinyl compound blockcopolymer (d) is not limited to those derived from the functionalityblock copolymer used in the preparation of the block copolymer (b), andcan include a block copolymer of an aromatic vinyl compound, aconjugated diene and another monomer copolymerizable with these. Thearomatic vinyl compound block copolymer (d) has preferably similarprofiles of the polymer block (I) in the block copolymer (b).

[0094] With respect to the aromatic vinyl compound block copolymer (d),the content of the structural unit derived from the aromatic vinylcompound is preferably in the range of 5 to 90% by weight, morepreferably 10 to 90% by weight, and still more preferably 20 to 80% byweight, based on the total structural unit of the aromatic vinylcompound block copolymer (d). In addition, in the aromatic vinylcompound block copolymer (d), the number average molecular weight of thearomatic vinyl compound polymer block and that of the conjugated dienepolymer block are not particularly limited, but the number averagemolecular weight of the aromatic vinyl compound polymer block preferablyranges from 2,500 to 100,000, and the number average molecular weight ofthe conjugated diene polymer block preferably ranges from 10,000 to250,000 before hydrogenation. Also, the number average molecular weightof the aromatic vinyl compound block copolymer (d) is in the range ofpreferably 15,000 to 500,000, and more preferably 20,000 to 400,000,before hydrogenation. Here, the number average molecular weight of thearomatic vinyl compound block copolymer (d) is a value obtained by gelpermeation chromatography [GPC], based on the standard polystyrenecalibration curve.

[0095] In the aromatic vinyl compound block copolymer (d), theconjugated diene polymer block may be hydrogenated partially orentirely. In this case, the hydrogenation ratio of the conjugated dienepolymer block is preferably 50 mol % or more, more preferably 60 mol %or more, and still more preferably 80 mol % or more, from the viewpointof heat resistance, weatherability and light resistance. The conjugateddiene polymer block in the aromatic vinyl compound block copolymer (d)is preferably at least one of the polymer block selected from the groupconsisting of a polyisoprene which may be hydrogenated, a polybutadienewhich may be hydrogenated and a copolymer of isoprene and butadienewhich may be hydrogenated.

[0096] In the aromatic vinyl compound block copolymer (d), the bondingform of the aromatic vinyl compound polymer block and the conjugateddiene polymer block may be linear, branched, radial or mixed typethereof. Preferably, they are bonded in linear form. The aromatic vinylcompound block copolymer (d) has preferably a structure in which two ormore of the aromatic vinyl compound polymer blocks and one or more ofthe conjugated diene blocks are bonded in linear form, and has morepreferably a tri-block structure in which two aromatic vinyl compoundpolymer blocks and one conjugated diene block are bonded in linear form.

[0097] The aromatic vinyl compound block copolymer (d) may have, on aterminal or in a molecular chain, a functional group such as hydroxylgroup, carboxyl group, acid anhydride group, epoxy group, amino group, ahalogen atom or mercapto group. The MFR [melt flow rate] value of thearomatic vinyl compound block copolymer (d), when measured at 230° C.under the load of 2.16 kg, is preferably not more than 100 g/10 minutes,more preferably not more than 50 g/10 minutes, and still more preferablynot more than 30 g/10 minutes. Here, the MFR value of the aromatic vinylcompound block copolymer (d) is measured in accordance with ASTMD-1238.In addition, the JIS A hardness of the aromatic vinyl compound blockcopolymer (d) falls preferably between 30 and 95, more preferablybetween 40 and 90, and still more preferably between 50 and 85. Here,the JIS A hardness of the aromatic vinyl compound block copolymer (d) ismeasured in accordance with JIS K-6253.

[0098] The amount of the aromatic vinyl compound block copolymer (d) ispreferably not more than 500 parts by weight, more preferably in therange of 0 to 300 parts by weight, based on 100 parts by weight of theblock copolymer (b).

[0099] The vinyl chloride polymer composition of the present inventioncan contain an ethylene-α-olefin copolymer(e). The ethylene-α-olefincopolymer (e) is disclosed in the International Patent ApplicationPublication No. 94/06859 [WO 94/06859]. It is known that theethylene-α-olefin copolymer (e) can be blended with a thermoplasticpolymer such as a polyolefin, a polyurethane or a polyvinyl chloride, inorder to improve the impact resistance of these resins at lowtemperature. By using such an ethylene-α-olefin copolymer (e), a vinylchloride polymer composition having more improved flexibility can beobtained.

[0100] The α-olefin unit which constitutes the ethylene-α-olefincopolymer (e) can include, for example, ones derived from an α-olefinsuch as propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene or1-octadecene. The ethylene-α-olefin copolymer (e) can include one ormore of these α-olefin units.

[0101] As the α-olefin unit, the preferred one is the structural unitderived from an α-olefin having 4 or more carbon atoms, the morepreferred one is the structural unit derived from an α-olefin having 6to 12 carbon atoms, the still more preferred one is the structural unitderived from an α-olefin having 6 to 10 carbon atoms, and the mostpreferred one is the structural unit derived from 1-hexene or 1-octene,because a vinyl chloride polymer composition having more improvedflexibility can be obtained.

[0102] The ethylene-α-olefin copolymer (e) can optionally have a slightamount of structural units derived from a non-conjugated diene. Such astructural unit includes, for example, ones derived from divinylbenzene,ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene,1,4-cyclohexadiene, cyclooctadiene and methylenenorbornene.

[0103] The molar ratio of the ethylene unit based on the α-olefin unit[ethylene unit/α-olefin unit], both of which constitute theethylene-α-olefin copolymer (e), falls preferably between 55/45 and99/1. When the molar ratio of the ethylene unit is lower than theabove-described range, the softening temperature of theethylene-α-olefin copolymer (e) becomes low, which is the cause of thetendency of the hang up of the resulting vinyl chloride polymercomposition. On the other hand, the molar ratio of the ethylene unit ishigher than the above-described range, it is difficult to produce avinyl chloride polymer composition having good flexibility. The molarratio of the ethylene unit based on the α-olefin unit [ethyleneunit/α-olefin unit] falls more preferably between 75/25 and 95/5, andstill more preferably between 80/20 and 95/5.

[0104] The MFR [melt flow rate] value of the ethylene-α-olefin copolymer(e), when measured at 190° C. under the load of 2.16 kg, is preferablyin the range of 0.1 to 100 g/10 minutes. By using an ethylene-α-olefincopolymer (e) having such an MFR value, a vinyl chloride polymercomposition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.The MFR [melt flow rate] value of the ethylene-α-olefin copolymer (e),when measured at 190° C. under the load of 2.16 kg, is more preferablyin the range of 0.2 to 70 g/10 minutes, and still more preferably in therange of 0.3 to 50 g/10 minutes. Here, the MFR value of theethylene-α-olefin copolymer (e) is measured in accordance with ASTMD-1238.

[0105] The Shore A hardness of the ethylene-α-olefin copolymer (e) fallspreferably between 30 and 90. By using an ethylene-α-olefin copolymer(e) having such a Shore A hardness, a vinyl chloride polymer compositionhaving excellent properties such as non-tackiness, flexibility,mechanical properties and processability can be obtained. The Shore Ahardness of the ethylene-α-olefin copolymer (e) falls more preferablybetween 40 and 85, and still more preferably between 45 and 80. Here,the Shore A hardness of the ethylene-α-olefin copolymer (e) is measuredin accordance with ASTM D-2240.

[0106] The density of the ethylene-α-olefin copolymer (e) is preferablyin the range of 0.80 to 0.95 g/cm³. By using an ethylene-α-olefincopolymer (e) having such a density, a vinyl chloride polymercomposition having excellent properties such as non-tackiness,flexibility, mechanical properties and processability can be obtained.The density of the ethylene-α-olefin copolymer (e) is more preferably inthe range of 0.82 to 0.93 g/cm³, and still more preferably in the rangeof 0.85 to 0.90 g/cm³. Here, the density of the ethylene-α-olefincopolymer (e) is measured in accordance with ASTM D-792.

[0107] The Mooney viscosity of the ethylene-α-olefin copolymer (e),measured at 100° C. with L type rotor, is preferably in the range of 5to 100 ML₁₊₄ (100° C.). By using an ethylene-α-olefin copolymer (e)having such a Mooney viscosity, a vinyl chloride polymer compositionhaving excellent properties such as non-tackiness, flexibility,mechanical properties and processability can be obtained. The Mooneyviscosity of the ethylene-α-olefin copolymer (e) is more preferably inthe range of 10 to 70 ML₁₊₄ (100° C.). Here, the Mooney viscosity of theethylene-α-olefin copolymer (e) is measured in accordance with ASTMD-1646.

[0108] The ethylene-α-olefin copolymer (e) is preferably used at aweight ratio, based on the weight of the vinyl chloride polymer (a) andthe block copolymer (b), to meet the following equations (2) and (3).

1/100≦Wb/(Wa+We)≦100/100  (2)

30/70≦Wa/We≦95/5  (3)

[0109] ; wherein Wa means the weight of the vinyl chloride polymer (a),Wb means the weight of the block copolymer (b) and We means the weightof the ethylene-α-olefin copolymer (e).

[0110] By using the ethylene-α-olefin copolymer (e) in theabove-described amount, a vinyl chloride polymer composition havingexcellent properties such as non-tackiness, flexibility, mechanicalproperties and processability can be obtained.

[0111] The weight ratio [Wa/We] of the ethylene-α-olefin copolymer (e)and the vinyl chloride polymer (a) is in the range of preferably 40/60to 90/10, and more preferably 50/50 to 85/15.

[0112] In addition, the weight ratio [Wb/(Wa+We)] of theethylene-α-olefin copolymer (e), the vinyl chloride polymer (a) and theblock copolymer (b) is in the range of preferably 2/100 to 60/100, morepreferably 3/100 to 40/100, and still more preferably 3/100 to 25/100.

[0113] The vinyl chloride polymer composition of the present inventioncan contain a paraffin oil (f).

[0114] As the paraffin oil (f), ones containing 60% by weight or more ofa paraffin ingredient [a linear hydrocarbon] are generally used. Thepreferred oil is the one containing 80% by weight or more of a paraffiningredient. The paraffin oil (f) can contain an ingredient having anaromatic ring such as benzene ring or naphthalene ring.

[0115] The dynamic viscosity of the paraffin oil (f) is in the range ofpreferably 20 to 800 cSt [mm²/s], and more preferably 50 to 60 cSt[mm²/s]. Here, the dynamic viscosity of the paraffin oil (f) is measuredin accordance with JIS K-2283.

[0116] Also, the current point of the paraffin oil (f) is in the rangeof preferably −40 to 0° C., and more preferably −30 to 0° C. Here, thecurrent point of the paraffin oil (f) is measured in accordance with JISK-2269.

[0117] In addition, the flash point of the paraffin oil (f) is in therange of preferably 200 to 400° C., and more preferably 250 to 300° C.Here, the flash point of the paraffin oil (f) is measured in accordancewith JIS K-2265.

[0118] By using a paraffin oil (f), a vinyl chloride polymer compositionhaving improved flexibility can be obtained. Further, by using aparaffin oil (f) together with the above-described aromatic vinylcompound block copolymer (d), the resulting vinyl chloride polymercomposition shows more improved flexibility and no migration of theparaffin oil.

[0119] The amount of the paraffin oil is, when used alone, preferablynot more than 100 parts by weight based on 100 parts by weight of theblock copolymer (b).

[0120] When the paraffin oil (f) is used together with the aromaticvinyl compound block copolymer (d), they are preferably used at a weightratio, based on the weight of the vinyl chloride polymer (a) and theblock copolymer (b), to meet the following equations (4), (5) and (6).

1/100≦Wb/(Wa+Wd+Wf)≦100/100  (4)

25/75≦Wd/Wf≦95/5  (5)

30/70≦Wa/(Wd+Wf)≦95/5  (6)

[0121] ; wherein Wa means the weight of the vinyl chloride polymer (a),Wb means the weight of the block copolymer (b), Wd means the weight ofthe aromatic vinyl compound block copolymer (d) and Wf means the weightof the paraffin oil (f).

[0122] By using the paraffin oil (f) and the aromatic vinyl compoundblock copolymer (d) in the above-described amount, a vinyl chloridepolymer composition having excellent non-tackiness and processabilityand having extremely excellent flexibility can be obtained.

[0123] The weight ratio [Wa/(Wd+Wf)] of the vinyl chloride polymer (a),the paraffin oil (f) and the aromatic vinyl compound block copolymer (d)is in the range of preferably 40/60 to 90/10, and more preferably 50/50to 85/15.

[0124] Also, the weight ratio [Wd/Wf] of the aromatic vinyl compoundblock copolymer (d) and the paraffin oil (f) is in the range ofpreferably 30/70 to 85/15, and more preferably 35/65 to 75/25.

[0125] In addition, the weight ratio [Wb/(Wa+Wd+Wf)] of the vinylchloride polymer (a), the block copolymer (b), the paraffin oil (f) andthe aromatic vinyl compound block copolymer (d) is in the range ofpreferably 2/100 to 60/100, more preferably 3/100 to 40/100, and stillmore preferably 3/100 to 25/100.

[0126] The vinyl chloride polymer composition of the present inventioncan optionally contain a styrene-based polymer (g) different from eitherof the block copolymer (b) or the aromatic vinyl compound blockcopolymer (d), within the extent where effects of the invention isretained. Also, the vinyl chloride polymer composition of the presentinvention can optionally contain an olefin-based polymer (h) other thanthe ethylene-α-olefin copolymer (e), within the extent where effects ofthe invention is retained. The amount of the styrene-based polymer (g)or the olefin-based polymer (h) is, in general, within the range ofpreferably 1 to 10% by weight based on the total weight of the vinylchloride polymer (a) and the block copolymer (b). By blending such astyrene-based polymer (g) or an olefin-based polymer (h), the resultingvinyl chloride polymer composition may sometimes show improvedproperties such as non-tackiness and processability.

[0127] As the styrene-based polymer (g), one having a structural unitderived from a styrene monomer in an amount of 10 by weight or more ispreferably used. The more preferred styrene-based polymer is that havinga structural unit derived from a styrene monomer in an amount of 50% byweight or more. The styrene monomer can include styrene,α-methylstyrene, p-methylstyrene, p-tert-butylstyrene,3,4-dimethylstyrene and the like. The styrene-based polymer (g) cancontain one or more of the structural units derived from such a styrenemonomer.

[0128] In addition, the styrene-based polymer (g) may contain astructural unit derived from a vinyl monomer other than theabove-mentioned styrene monomer. Examples of the vinyl monomer otherthan the styrene monomer can include ones having a cyano group such asacrylonitrile and methacrylonitrile; C1-18 alkyl esters of acrylic acidor C1-18 alkyl esters of methacrylic acid such as methyl esters, ethylesters, propyl esters, n-butyl esters, isobutyl esters, hexyl esters,2-ethylhexyl esters, dodecyl esters and octadecyl esters; esters ofacrylic acid or methacrylic acid and a diol such as ethylene glycol,propylene glycol or butanediol; vinyl esters of a carboxylic acid having1 to 6 carbon atoms such as acetic acid or propionic acid; unsaturatedcarboxylic acids such as acrylic acid, methacrylic acid and maleic acid;unsaturated dicarboxylic anhydrides such as maleic anhydride;(meth)acrylamides such as acrylamide, methacrylamide andN,N-dimethylacrylamide; maleimide; N-substituted maleimides such asN-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide andN-cyclohexylmaleimide; conjugated dienes such as butadiene and isoprene;and so on. The styrene-based polymer (g) may contain one or more of thestructural units derived from such a vinyl monomer.

[0129] The olefin-based polymer (h) includes homopolymers of an olefinsuch as ethylene, propylene or butylene; copolymers of two or more ofthe above-mentioned olefins; and copolymers of one or more of theabove-mentioned olefins and one or more of other vinyl monomers.Examples of the olefin-based polymer (h) can include low-densitypolyethylenes, medium-density polyethylenes, high-density polyethylenes,polypropylenes, polybutylenes, ethylene-vinyl acetate copolymers,ethylene-acrylic acid copolymers, ethylene-maleic anhydride copolymers,propylene-acrylic acid copolymers, propylene-maleic anhydridecopolymers, isobutylene-maleic anhydride copolymers and the like. One ormore of these olefin homopolymers or olefin copolymers can be used asthe olefin-based polymer (h).

[0130] In addition, a styrene-based polymer (g) and an olefin-basedpolymer (h) can be used together, if required.

[0131] The vinyl chloride polymer composition of the present inventioncan optionally contain a thermosetting polyurethane resin, a polyamideresin, a polyester resin, a polyvinylidene chloride resin, apolycarbonate resin, an acrylic resin or a polyoxymethylene resin,within the extent where effects of the invention is retained.

[0132] In addition, the vinyl chloride polymer composition of thepresent invention can optionally contain an additional component,examples of which include stabilizers for the vinyl chloride polymer (a)such as metallic soaps of calcium stearate, zinc stearate, bariumstearate, cadmium stearate and lead stearate; inorganic stabilizers suchas dibasic sulfates, dibasic lead stearate, calcium hydroxide andcalcium silicate; additives such as lubricants, pigments, impactmodifiers, processing materials, nucleating agents, reinforcing agents,colorants, flame retardants, weatherability modifiers, ultravioletabsorbents, antioxidants, hydrolysis inhibitors, antifungal agents,light stabilizers, antistatic agents, a silicone oil, anti-blockingagents, forming agents and perfumes; fibers such as glass fibers andpolyester fibers; fillers such as talc, silica and wood powder; variouscoupling agents, and the like.

[0133] The vinyl chloride polymer composition of the present inventioncan be produced by a process in which the above-described components canbe uniformly blended. Among them, a melt kneading process is simple andpreferred.

[0134] The vinyl chloride polymer composition of the present inventioncan be produced by, for example, melt kneading the respective componentswith a melt kneading machine such as a single-screw extruder, atwin-screw extruder, a kneading machine, a mixing roll or a Banburymixer, generally at a temperature of 120 to 220° C. for about 30 secondsto 5 minutes. The blending sequence of the respective components has noparticular restriction on melt kneading.

[0135] The vinyl chloride polymer composition of the present inventioncan be produced, for example, by the following procedures.

[0136] [I] The production of a composition containing a vinyl chloridepolymer (a) and a block copolymer (b).

[0137] (I-1) A vinyl chloride polymer (a) and a block copolymer (b) [orthe above-described block copolymer composition] are simultaneously fedinto a melt kneading machine for kneading.

[0138] (I-2) A block copolymer (b) [or the above-described blockcopolymer composition] is produced by melt kneading, to which a vinylchloride polymer (a) is added, for melt kneading, therewith.

[0139] (I-3) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of a vinyl chloride polymer (a).

[0140] [II] The production of a composition containing a vinyl chloridepolymer (a), a block copolymer (b) and an ethylene-α-olefin copolymer(e).

[0141] (II-1) A vinyl chloride polymer (a), an ethylene-α-olefin.copolymer (e) and a block copolymer (b) [or the above-described blockcopolymer composition] are simultaneously fed into a melt kneadingmachine for kneading.

[0142] (II-2)An ethylene-α-olefin copolymer (e) and a block copolymer(b) [or the above-described block copolymer composition] aremelt-kneaded to give a composition. Then, the resulting composition anda vinyl chloride polymer (a) are melt-kneaded.

[0143] (II-3) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of a vinyl chloride polymer (a) and an ethylene-α-olefincopolymer (e).

[0144] (II-4) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of an ethylene-α-olefin copolymer (e). Then, the resultingcomposition and a vinyl chloride polymer (a) are melt-kneaded.

[0145] [III] The production of a composition containing a vinyl chloridepolymer (a), a block copolymer (b), a paraffin oil (f) and an aromaticvinyl compound block copolymer (d).

[0146] (III-1) A vinyl chloride polymer (a), an aromatic vinyl compoundblock copolymer (d), a paraffin oil (f) and a block copolymer (b) [orthe above-described block copolymer composition] are simultaneously fedinto a melt kneading machine for kneading.

[0147] (III-2) An aromatic vinyl compound block copolymer (d), aparaffin oil (f) and a block copolymer (b) [or the above-described blockcopolymer composition] are melt-kneaded to give a composition. Then, theresulting composition and a vinyl chloride polymer (a) are melt-kneaded.

[0148] (III-3) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of an aromatic vinyl compound block copolymer (d). To theresulting composition, a paraffin oil (f) is blended, and then a vinylchloride polymer (a) is melt-kneaded therein.

[0149] (III-4) A vinyl chloride polymer (a), an aromatic vinyl compoundblock copolymer (d) and a block copolymer (b) [or the above-describedblock copolymer composition] are melt-kneaded to give a composition.Then, to the resulting composition, a paraffin oil (f) is blended.

[0150] (III-5) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of a vinyl chloride polymer (a) and an aromatic vinyl compoundblock copolymer (d). Then, to the resulting composition, a paraffin oil(f) is blended.

[0151] (III-6) A vinyl chloride polymer (a), an aromatic vinyl compoundblock copolymer (d) and a paraffin oil (f) are melt-kneaded to give acomposition. Then, the resulting composition and a block copolymer (b)[or the above-described block copolymer composition] are melt-kneaded.

[0152] (III-7) A vinyl chloride polymer (a) and a block copolymer (b)[or the above-described block copolymer composition] are melt-kneaded togive a composition. Then, to the resulting composition, an aromaticvinyl compound block copolymer (d) and a paraffin oil (f) are suppliedfor melt kneading.

[0153] (III-8) The production of a block copolymer (b) [or theabove-described block copolymer composition] is carried out in thepresence of a vinyl chloride polymer (a). Then, to the resultingcomposition, an aromatic vinyl compound block copolymer (d) and aparaffin oil (f) are supplied for melt kneading.

[0154] (III-9) A vinyl chloride polymer (a) and an aromatic vinylcompound block copolymer (d) are melt-kneaded to give a composition.Then, to the resulting composition, a paraffin oil (f) and a blockcopolymer (b) [or the above-described block copolymer composition] aresupplied for melt kneading.

[0155] (III-10) A paraffin oil (f) is blended with a block copolymer (b)[or the above-described block copolymer composition] to give acomposition. Then, to the resulting composition, a vinyl chloridepolymer (a) and an aromatic vinyl compound block copolymer (d) aresupplied for melt kneading.

[0156] (III-11) A paraffin oil (f) is blended with an aromatic vinylcompound block copolymer (d) to give a composition. Then, to theresulting composition, a vinyl chloride polymer (a) and a blockcopolymer (b) [or the above-described block copolymer composition] aresupplied for melt kneading.

[0157] (III-12) A composition containing a vinyl chloride polymer (a)and a block copolymer (b) [or the above-described block copolymercomposition], and a composition containing an aromatic vinyl compoundblock copolymer (d) and a paraffin oil (f) are respectively prepared.Then, two kinds of the resulting compositions are melt-kneaded.

[0158] (III-13) A composition containing a vinyl chloride polymer (a)and an aromatic vinyl compound copolymer (d), and a compositioncontaining a block copolymer (b) [or the above-described block copolymercomposition] and a paraffin oil (f) are respectively prepared. Then, twokinds of the resulting compositions are melt-kneaded.

[0159] A thermoplastic polyurethane (c), a styrene-based polymer (g), anolefin-based polymer (h) and the above-described additional componentsmay be blended during the preparation or after the preparation of thevinyl chloride polymer composition. When they are blended during thepreparation of the vinyl chloride polymer composition, the thermoplasticpolyurethane (c), the styrene-based polymer (g), the olefin-basedpolymer (h) or the above-described additional components may be fed intoa melt kneading machine for kneading separately from the vinyl chloridepolymer (a), the block copolymer (b) [or the above-described blockcopolymer composition], the ethylene-α-olefin copolymer (e), theparaffin oil (f) and the aromatic vinyl compound block copolymer (d).Alternatively, they can be fed into a melt kneading machine for kneadingas a compound with at least one of the vinyl chloride polymer (a), theblock copolymer (b) [or the above-described block copolymercomposition], the ethylene-α-olefin copolymer (e), the paraffin oil (f)and the aromatic vinyl compound block copolymer (d). In the preferredembodiments, they are fed into a melt kneading machine for kneading as acompound with the block copolymer (b) [or the above-described blockcopolymer composition].

[0160] The vinyl chloride polymer composition of the present inventioncan be subjected to a melt molding or a thermal processing. By using avinyl chloride polymer composition of the present invention, a varietyof articles can be obtained smoothly by various molding methods such asextrusion molding, injection molding, press molding, blow molding,calendar molding, casting, and so on. The vinyl chloride polymercomposition of the present invention can give a molded article havingexcellent properties such as non-tackiness, flexibility and mechanicalproperties.

[0161] By taking advantages of the above-described characteristics, thevinyl chloride polymer composition of the present invention can beapplied for various uses including, for example, various household goodssuch as raincoats, umbrellas, rain pants, rain shoes and caps; variouskeyboards; laminates; various films or sheets for various containers;agricultural articles such as plastic hothouses; sheet forming productssuch as handbags, wallets and stationery; footwear articles such assandal bands and slippers; belts; interior decorative articles such aswall covering materials and cushiony floors; toys such as dolls andfloats; leather goods for automobiles, for furniture, for bags or forapparel; wire covering materials; extruded products such as gas pipes,hoses, and tubes; automobile components such as steering wheels; machineparts; watchbands; and packing materials.

[0162] Further, the vinyl chloride polymer composition of the presentinvention has, in addition to the above-described characteristics,excellent melt-adhesiveness to various materials and, therefore, can befirmly adhered, under it's molten state, to various other materialsincluding, for example, synthetic resins, rubbers, metals, woods,ceramics, paper, and fabrics. Thus, the vinyl chloride polymercomposition of the present invention can be effectively used,especially, for the production of composite articles with a membercomprising such other materials.

[0163] Examples of such other materials include various thermoplasticresins, various compositions comprising thermoplastic resins other thanthe vinyl chloride polymer composition of the present invention,thermosetting resins, papers, fabrics, metals, woods, ceramics and thelike.

[0164] The vinyl chloride polymer composition of the present inventionis excellent in melt-adhesiveness particularly to the materials havingpolarity. Examples of the materials having polarity include polyurethaneresins; polyamide resins; polyester resins; polyvinylidene chlorideresins; polyvinyl chloride resins; vinyl chloride-vinyl acetatecopolymers; epoxy resins; polycarbonate resins; polyphenylenesulfideresins; (meth)acrylic resins; polyoxymethylene resins; polysulfoneresins; saponified ethylene-vinyl acetate copolymers; resins such ascopolymers of aromatic vinyl compounds and vinyl cyanide compounds orcompositions containing them; various synthetic rubbers such asbutadiene-acrylonitrile rubbers, chloroprene rubbers, urethane rubbers,silicone rubbers, fluorocarbon rubbers and acrylonitrile rubbers; andvarious metals such as iron, aluminum and copper.

[0165] The composite articles are typically laminate structures such asfilms and sheets. They can include tubes, profiles and articles havingvarious three-dimensional forms.

[0166] The laminate structures comprising the vinyl chloride polymercomposition of the present invention has no particular restriction onthe number of layers, the thickness of each layer, the shape, theconfiguration and the like, which can be appropriately adjustedaccording to the intended purpose of the laminate and so on.

[0167] Representative examples of the laminate structures comprising thevinyl chloride polymer composition of the present invention include, butare not limited thereto, a two-layered laminate structure having a layerof the vinyl chloride polymer composition of the present invention and alayer of another material, a three-layered laminate structure having ainner layer of the vinyl chloride polymer composition of the presentinvention between two outer layers [surface layers] of other materials,a three-layered laminate structure where two layers of the vinylchloride polymer composition of the present invention are laminated onboth surfaces of a layer of another material, or a four or more-layeredlaminate structure in which a layer of the vinyl chloride polymercomposition of the present invention and a layer of one or more of othermaterials are alternately stacked.

[0168] When the laminate structure has two or more of the layers ofother materials, each material may be the same or different. Inaddition, when the laminate structure has two or more of the layers ofthe vinyl chloride polymer composition of the present invention eachvinyl chloride polymer composition of the present invention may be thesame or different.

[0169] The composite articles can be produced by a process in which amelt-adhesiveness is utilized. Examples of the process include meltmolding methods of injection moldings such as insert injection molding,two-color injection molding, core back injection molding, sandwichinjection molding and injection press molding; extrusion moldings suchas T-die laminate molding, co-extrusion molding, extrusion coating andprofile extrusion; blow molding; calendar molding; press molding; meltcasting and the like.

[0170] When the composite articles are produced by insert injectionmolding, the following process is generally employed. Namely, othermaterial, previously prepared, having a prescribed shape and size isdisposed in a mold, and the vinyl chloride polymer composition of thepresent invention is injected therein to give a composite article havinga member comprising the vinyl chloride polymer composition of thepresent invention and a member comprising the other material. In thiscase, there is no particular restriction on the preparation method forthe other material to be disposed in a mold. When the other material tobe disposed in a mold is the material comprising a synthetic resin or arubber, it is possible to employ various molding methods of, forexample, injection molding, extrusion molding, press molding andcasting. Whereas, when the other material to be disposed in a mold isthe material comprising a metal, it is possible to employ, for example,the methods generally applied for the manufacture of a metal product,such as casting, rolling, cutting, machining and grinding.

[0171] When the composite articles are produced by two-color injectionmolding, the following process is generally employed. Namely, the othermaterial is injected into a mold to form a member, then the cavity plateis exchanged, for example, by the rotation or the movement of the mold,and the vinyl chloride polymer composition of the present invention isinjected into the gap between the member comprising the other materialand the second mold plate to give a composite article. In this process,two or more of injection molding machines are employed.

[0172] Whereas, when the composite articles are produced by core backinjection molding, the following process is generally employed. Namely,by the use of one injection molding machine and one mold, the othermaterial is injected into the mold to form a member, then the cavity ofthe mold is enlarged, and the vinyl chloride polymer composition of thepresent invention is injected therein to give a composite article.

[0173] Alternatively, the composite articles may be produced in thefollowing manner. Namely, in the above-described injection moldings, theinjection sequence of the components is exchanged. Thus, the vinylchloride polymer composition of the present invention is first injectedinto the mold to form a member, and the other material such as athermoplastic resin is injected therein.

[0174] When the composite articles are produced by extrusion moldings,the following process or the like is generally employed. Namely, thevinyl chloride polymer composition of the present invention and theother material such as a thermoplastic resin are simultaneouslymelt-extruded and joined to each other, through a die [extrusion dieportion, or the like] divided into not less than two parts, examples ofwhich are the inner side and the outer side, the upper side and thelower side, or the left-hand side and the right-hand side. If the othermaterial is not a thermoplastic material, the composite articles can beproduced by extrusion coating of the vinyl chloride polymer compositionof the present invention to above or around the other material.

[0175] Further, when the composite articles are produced by calendarmolding, they can be produced by the calendar coating of the vinylchloride polymer composition of the present invention at a molten stateonto the other material which may be in the molten and plastic state, orin the solid state.

[0176] Still further, when the composite articles are produced by pressmolding, they can be produced by the melt pressing of the vinyl chloridepolymer composition of the present invention with the disposed othermaterial.

[0177] The composite articles comprising the vinyl chloride polymercomposition of the present invention can be applied for various usessuch as industrial goods according to the kind of the other material orthe characteristics of the member comprising the vinyl chloride polymercomposition or the other material. The composite articles can be appliedfor various kinds of interior automotive trims such as instrumentpanels, center panels, center console boxes, door trims, pillars, assistgrips, steering wheels and airbag covers; automobile exterior parts suchas protector moldings and bumpers; electrical household parts such asbumpers of vacuum cleaners, door stops of the refrigerator, cameragrips, electrical machinery grips, remote control switches and variouskinds of key tops of office automation equipments; sports goods such asswimming goggles; various kinds of cover parts; various industrialcomponents with packing for the use of sealing, sound insulation orvibration damping; electronic parts such as curled cord wire coverings;various films for food, medical care, agriculture and packaging;building materials such as door stops, window frames, wall papers anddecorative laminates; electrical and electronic parts such as belts,hoses, tubes, mats, sheets and soundness gears; various joints andvalves.

EXAMPLES

[0178] The present invention will be explained more specifically withreference to examples but the present invention is not restricted at allto such examples.

[0179] In the following Examples and Comparative Examples, the hardness,the non-tackiness, the flexibility and the mechanical properties [yieldstrength and elongation at yield point] of the molded articlescomprising the vinyl chloride polymer composition, and the adhesionstrength in the laminate structure comprising the vinyl chloride polymercomposition were measured and evaluated according to the followingmethods.

[0180] (1) Hardness

[0181] Each vinyl chloride polymer composition obtained in Examples andComparative Examples was molten at 150° C. for 2 minutes by means of apress molding machine [“compression molding machine AYS-10”, trade name,made by Shinto Metal Industries, Ltd.]. Then, the molten product washeld under the load of 50 kgf at 150° C. for 30 seconds to give a moldedarticle [test piece] with a thickness of about 2 mm.

[0182] Two of the molded articles [test pieces] were stacked one onanother, and tested for the Shore A hardness of the molded article [testpiece] in accordance with the method of JIS K-6301.

[0183] (2) Non-Tackiness

[0184] Fifty plates of the molded articles [test pieces] obtained in theabove-described test method (1) were stacked into one piece withoutreleasing paper, and allowed to stand at room temperature for 1 week.Then, the degree of tackiness between the molded articles when they werepeeled off one by one was observed, so that the non-tackiness wasevaluated according to the following standards.

[0185] Evaluation Standards of Non-Tackiness

[0186] ◯: The molded articles can be easily and smoothly peeled off oneby one, because no sticking occurs.

[0187] Δ: A sticking is observed. However, the molded articles can bepeeled off with a force application.

[0188] X: It is impossible for the molded articles to be peeled off oneby one even with a force application, because they are firmly stuck toeach other.

[0189] (3) Flexibility

[0190] The molded article [test piece] obtained in the above-describedtest method (1) was allowed to stand at 25° C. for 2 days. Then, it wasbent to 180 degrees. The bent portion was visually observed andevaluated according to the following standard. Here, the whitening onbending corresponds to the occurrence of boundary separation.

[0191] Evaluation Standards of Flexibility

[0192] ⊚: No change is observed, and the flexibility is good

[0193] ◯: Whitening on bending is slightly observed at the bent portion.

[0194] X: Remarkable whitening on bending is observed at the bentportion.

[0195] (4) Mechanical Properties [Yield Strength and Elongation at YieldPoint]

[0196] The molded article [test piece] obtained in the above-describedtest method (1) was allowed to stand at 25° C. for 2 days. Then, it waspunched into JIS No. 3 Dumbbell shape and tested for the yield strengthand the elongation at yield point using “Autograph IS-500D” [trade name,made by Shimadzu Corporation] under the condition of a tensile speed of300 mm/minutes at room temperature according to the method of JISK-7311.

[0197] (5) Adhesion Strength in a Laminate Structure

[0198] The vinyl chloride polymer composition obtained in Examples orComparative Examples was stacked on a molded article [thickness of 2 mm]of a rigid polyvinyl chloride resin composition [PVC-C] shown below.Then, they were molten at 170° C. for 2 minutes with a press moldingmachine [“compression molding machine “AYS-10”, trade name, made byShinto Metal Industries, Ltd.] and press bonded to each other under theload of 50 kgf at 170° C. for 30 seconds to give a laminate structure.

[0199] The resulting laminate structure was cut into a test piece [size:1 cm×8 cm] and tested for the adhesion strength between a layer of thevinyl chloride polymer composition, obtained in Examples or ComparativeExamples, and a layer of the rigid polyvinyl chloride resin compositionaccording to a 180 degrees peeling test using “Autograph IS-500D” [tradename, made by Shimadzu Corporation] under the condition of a peelingspeed of 300 mm/minutes at room temperature.

[0200] When the adhesion strength between the layers is very strong andthe respective layers cannot be peeled resulting to the failure ofconducting the peeling test, it is evaluated as “Impossible to peel”. Onthe other hand, when the adhesion strength between the layers is veryweak and the respective layers can be readily delaminated by hands, itis evaluated as “Readily peeled”.

[0201] (6) Non-Migration

[0202] The molded article [test piece] obtained in the above-describedtest method (1) was stacked on a molded article [thickness of 2 mm] ofthe rigid polyvinyl chloride resin composition, and the stack wasallowed to stand under the load of 0.5 kgf at 70° C. for 24 hours. Afterthe molded articles were separated from each other, the presence orabsence of migration substances onto the surface of the molded articleof the rigid polyvinyl chloride resin composition was visually observed.The one which showed no trace of migration was evaluated as “◯” whilethe one which showed a trace of migration was evaluated as “X”.

[0203] Abbreviations and properties of the compounds as referred to inthe following Examples and Comparative Examples are as follows.

[0204] [Vinyl Chloride Polymer]

[0205] PVC: Polyvinyl chloride having a degree of polymerization of1,000 [“TK 1000”, trade name, made by Shin-Etsu Chemical Co., Ltd.]

[0206] [Rigid Polyvinyl Chloride Resin Compound]

[0207] PVC-C: A rigid polyvinyl chloride resin compound comprising 100parts by weight of the polyvinyl chloride having a degree ofpolymerization of 1,000, 15 parts by weight of a copolymer of methylmethacrylate, butadiene and styrene [MBS resin; “Metablen C-303A”, tradename, made by Mitsubishi Rayon Co., Ltd.], 2 parts by weight of anorganic tin stabilizer [“KS-1000”, trade name, made by Kyodo ChemicalCo., Ltd.] and 1.5 parts by weight of a lubricant [“Wax OP”, trade name,Clariant (Japan) K.K.].

[0208] [Ethylene-α-olefin Copolymers]

[0209] POE-A: Ethylene-1-octene copolymer [“ENGAGE EG8200”, trade name,made by DuPont Dow Elastomers Limited; Ethylene unit/1-octene unit=92/8(molar ratio); MFR (at 190° C., under the load of 2.16 kg): 4.2 g/10minutes; Shore A hardness: 75; Density: 0.870 g/cm³; Mooney viscosity:12.1 ML₁₊₄ (100° C.)]

[0210] POE-B: Ethylene-1-octene copolymer [“ENGAGE EG8842”, trade name,made by DuPont Dow Elastomers Limited; Ethylene unit/1-octene unit=83/17(molar ratio); MFR (at 190° C., under the load of 2.16 kg): 1.0 g/10minutes; Shore A hardness: 51; Density: 0.857 g/cm³; Mooney viscosity:37.2 ML₁₊₄ (100° C.)]

[0211] POE-C: Ethylene-1-octene copolymer [“ENGAGE EG8100”, trade name,made by DuPont Dow Elastomers Limited; Ethylene unit/1-octene unit=93/7(molar ratio); MFR (at 190° C., under the load of 2.16 kg): 1.0 g/10minutes; Shore A hardness: 75; Density: 0.870 g/cm³; Mooney viscosity:35.6 ML₁₊₄ (100° C.)]

[0212] [Functionality Block Copolymers]

[0213] F-SEEPS: Hydrogenated tri-block copolymer having a hydroxyl groupon one terminal of the molecule comprising polystyrene block-copolymerblock of isoprene and butadiene-polystyrene block [number averagemolecular weight: 50,000, styrene content: 30% by weight, hydrogenationratio in the copolymer block of isoprene and butadiene: 98%, molar ratioof isoprene and butadiene: 50/50, 1,2- and 3,4-bond content in thecopolymer block of isoprene and butadiene: 8 mol %, average number ofhydroxyl group per molecule: 0.9], which was prepared by using styrene,isoprene and butadiene as raw materials according to the methoddescribed in the Referential Example 1 of the Japanese PatentApplication Laid-open No. Hei 10-139963.

[0214] F-SEEPS consists “SEEPS-OH” which is a hydrogenated tri-blockcopolymer having a hydroxyl group on one terminal of the moleculecomprising polystyrene block-copolymer block of isoprene andbutadiene-polystyrene block [number average molecular weight: 50,000,styrene content: 30% by weight, hydrogenation ratio in the copolymerblock of isoprene and butadiene: 98%, molar ratio of isoprene andbutadiene: 50/50, 1,2- and 3,4-bond content in the copolymer block ofisoprene and butadiene: 8 mol %] and “SEEPS-1” which is a hydrogenatedtri-block copolymer having no hydroxyl group on the molecule comprisingpolystyrene block-copolymer block of isoprene and butadiene-polystyreneblock [number average molecular weight: 50,000, styrene content: 30% byweight, hydrogenation ratio in the copolymer block of isoprene andbutadiene: 98%, molar ratio of isoprene and butadiene: 50/50, 1,2- and3,4-bond content in the copolymer block of isoprene and butadiene: 8 mol%] at a molar ratio of SEEPS-OH/SEEPS-1=9/1.

[0215] F-HVSIS: Hydrogenated tri-block copolymer having a hydroxyl groupon one terminal of the molecule comprising polystyreneblock-polyisoprene block-polystyrene block [average number of hydroxylgroup per molecule: 0.8, styrene content: 25% by weight, number averagemolecular weight: 80,000, hydrogenation ratio in the polyisoprene block:85%, 1,4-bond content in the polyisoprene block: 45 mol %, 1,2- and3,4-bond content in the polyisoprene block: 55 mol %, MFR value (at 230°C., under the load of 2.16 kg): 6 g/10 minutes].

[0216] F-HVSIS consists “HVSIS-OH” which is a hydrogenated tri-blockcopolymer having a hydroxyl group on one terminal of the moleculecomprising polystyrene block-polyisoprene block-polystyrene block[number average molecular weight: 80,000, styrene content: 25% byweight, hydrogenation ratio in the polyisoprene block: 85%, 1,4-bondcontent in the polyisoprene block: 45 mol %, 1,2- and 3,4-bond contentin the polyisoprene block: 55 mol %] and “HVSIS” which is a hydrogenatedtri-block copolymer having no hydroxyl group on the molecule comprisingpolystyrene block-polyisoprene block-polystyrene block [number averagemolecular weight: 80,000, styrene content: 25% by weight, hydrogenationratio in the polyisoprene block: 85%, 1,4-bond content in thepolyisoprene block: 45 mol %, 1,2- and 3,4-bond content in thepolyisoprene block: 55 mol %] at a molar ratio of HVSIS-OH/HVSIS=8/2.

[0217] F-HVSIS was prepared by, according to the method described in theReferential Example 2 of the Japanese Patent Application Laid-open No.Hei 7-118492, polymerizing styrene and isoprene successively under thepresence of tetramethylethylenediamine in cyclohexane using sec-butyllithium followed by the addition of ethylene oxide to give a blockcopolymer having a hydroxyl group at the terminal of the molecule, andsubjecting the block copolymer to hydrogenation using a Zieglercatalyst.

[0218] [Aromatic Vinyl Compound Block Copolymers]

[0219] SEPS: Hydrogenated tri-block copolymer comprising polystyreneblock-polyisoprene block-polystyrene block [“Septon 2002”, trade name,made by KURARAY Co., Ltd.]

[0220] SEEPS-2: Hydrogenated tri-block copolymer comprising polystyreneblock-copolymer block of isoprene and butadiene-polystyrene block[“Septon 4033”, trade name, made by KURARAY Co., Ltd.]

[0221] [Paraffin Oil]

[0222] PL: Paraffin type of process oil [“Diana Process Oil PW-380”,trade name, made by IDEMITSU KOSAN CO., LTD.; Dynamic viscosity: 381.6cSt (40° C.); current point: −15° C.; flash point: 300° C.]

[0223] [Thermoplastic Polyurethane]

[0224] TPU: A polyurethane having a content of nitrogen atom of 1.9% byweight prepared by 1,4-butnediol, 4,4′-diphenylmethane diisocyanate anda polyester diol having a number average molecular weight of 3,500 whichis obtained by the reaction of 3-methyl-1,5-pentanediol and adipic acid.This TPU was prepared according to the method described in the Example 2of the Japanese Patent Application Laid-open No. Sho 47-34494.

[0225] [High Polymer Polyol]

[0226] POH-1: Polyester diol having a number average molecular weight of3,500 prepared by the reaction of 3-methyl-1,5-pentanediol and adipicacid [“Kuraray Polyol P-3500”, trade name, made by KURARAY Co., Ltd.]

[0227] [Chain Extender]

[0228] BD: 1,4-butanediol

[0229] [Organic Diisocyanate]

[0230] MDI: 4,4′-diphenylmethane diisocyanate

[0231] [Catalyst for Polyurethane Forming Reaction]

[0232] CAT: Dibutyltin diacetate

[0233] The “PU/SEEPS” prepared by the following Referential Example wasused as the block copolymer (b).

Referential Example 1

[0234] 100 parts by weight of the TPU and 100 parts by weight of theF-SEEPS were premixed. The resulting mixture was melt-kneaded using atwin-screw extruder [“BT-30”, trade name, made by Research Laboratory ofPlastics Technology Co., Ltd.; 30 mm φ; L/D=36] with coaxial screws,under the conditions of a cylinder temperature of 220° C. and a screwrotation speed of 150 rpm. The reaction mixture in melt was continuouslyextruded into water as a strand, and the resulting strands were cut inpellets with a palletizing machine. The resulting pellets were dried at80° C. for 4 hours to give a block copolymer compound A [PU-SEEPSCompound A].

[0235] From the block copolymer composition A [PU-SEEPS Compound A], thepolyurethane contained therein was extracted with dimethylformamide; andthereafter, the SEEPS-1 and the unreacted SEEPS-OH were extracted withcyclohaxane. The remaining solid was dried to give a block copolymer.¹H-NMR analysis showed that the block copolymer was a di-block copolymerhaving one polymer block (I) comprising polystyrene block-hydrogenatedcopolymer block of isoprene and butadiene-polystyrene block and onepolymer block (II) comprising a polyurethane ofpoly(3-methyl-1,5-pentanediol adipate) unit, 4,4′-diphenylmethanediisocyanate unit and 1,4-butanediol unit. The block copolymer isreferred to as “PU/SEEPS”.

[0236] The amounts of the polyurethane, which was extracted withdimethylformamide, the SEEPS-OH and the SEEPS-1, which were extractedwith cyclohexane, were 82.5 parts by weight of the polyurethane, 55parts by weight of the SEEPS-OH and 12.5 parts by weight of the SEEPS-1,respectively, based on 100 parts by weight of the PU/SEEPS.

[0237] The polymer block (I) of the PU/SEEPS had the same profiles asthose of the SEEPS-1.

Example 1

[0238] The PU/SEEPS was molten at 140° C. under nitrogen with a kneadingmachine [“Labo Plastomill 20R200”, trade name, made by Toyo SeikiSeisaku-sho Ltd]. To the resulting melt, the PVC was blended in anamount shown in Table 1. The resulting blend was melt-kneaded at atemperature of 140° C. and a mill rotation speed of 40 rpm undernitrogen for 5 minutes to give a vinyl chloride polymer composition.

[0239] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 1.

[0240] Comparative Examples 1 and 2

[0241] F-SEEPS or SEPS was molten at 140° C. under nitrogen with akneading machine [“Labo Plastomill 20R200”, trade name, made by ToyoSeiki Seisaku-sho Ltd]. To the resulting melt, the PVC was blended in anamount shown in Table 1. The resulting blend was melt-kneaded at atemperature of 140° C. and a mill rotation speed of 40 rpm undernitrogen for 5 minutes to give a vinyl chloride polymer composition.

[0242] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 1.

Example 2

[0243] The block copolymer compound A [PU-SEEPS Compound A] obtained inthe Referential Example 1 was molten at 140° C. under nitrogen with akneading machine [“Labo Plastomill 20R200”, trade name, made by ToyoSeiki Seisaku-sho Ltd]. To the resulting melt, the PVC was blended in anamount shown in Table 1. The resulting blend was melt-kneaded at atemperature of 140° C. and a mill rotation speed of 40 rpm undernitrogen for 5 minutes to give a vinyl chloride polymer composition.

[0244] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 1. TABLE 1Comparative Examples Examples 1 2 1 2 Composition [Part by weight] PVC60 50 50 50 PU/SEEPS 40 PU-SEEPS Compound A 50 F-SEEPS 50 SEPS 50Properties of the molded article Hardness [Shore A] 94 93 93 94Non-tackiness ◯ ◯ ◯ ◯ Flexibility ⊚ ⊚ ◯ ◯ Mechanical properties Yieldstrength [kgf/cm²]   150¹⁾    125¹⁾  70 64 Elongation at yield   150¹⁾   150¹⁾  67 70 point [%] Non-migration ◯ ◯ ◯ ◯ Adhesion strength ofImpossible Impossible Impossible Impossible the laminate structure topeel to peel to peel to peel Adhesion strength [kgf/cm]

Examples 3 to 5

[0245] The PU/SEEPS and the POE-A or the POE-B were premixed in anamount shown in Table 2. The resulting mixture was molten at 140° C.under nitrogen witha kneading machine [“Labo Plastomill 20R200”, tradename, made by Toyo Seiki Seisaku-sho Ltd]. To the resulting melt, thePVC was blended in an amount shown in Table 2. The resulting blend wasmelt-kneaded at a temperature of 140° C. and a mill rotation speed of 40rpm under nitrogen for 5 minutes to give a vinyl chloride polymercomposition.

[0246] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 2.

Comparative Examples 3 and 4

[0247] The POE-A or the POE-B was molten at 140° C. under nitrogen witha kneading machine [“Labo Plastomill 20R200”, trade name, made by ToyoSeiki Seisaku-sho Ltd]. To the resulting melt, the PVC was blended in anamount shown in Table 2. The resulting blend was melt-kneaded at atemperature of 140° C. and a mill rotation speed of 40 rpm undernitrogen for 5 minutes to give a vinyl chloride polymer composition.

[0248] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 2.

Examples 6 and 7

[0249] The block copolymer composition A [PU-SEEPS Compound A] obtainedin the Referential Example 1 and the POE-A or the POE-C were premixed inan amount shown in Table2. The resulting premix was molten at 140° C.under nitrogen with a kneading machine [Labo Plastomill 20R200”, tradename, made by Toyo Seiki Seisaku-sho Ltd]. To the resulting melt, thePVC was blended in an amount shown in Table 2. The resulting blend wasmelt-kneaded at a temperature of 140° C. and a mill rotation speed of 40rpm under nitrogen for 5 minutes to give a vinyl chloride polymercomposition.

[0250] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 2. TABLE 2Comparative Examples Examples 3 4 5 6 7 3 4 Composition [Part by weight]PVC 100  100  100  100  100  100  100  POE-A 100  100  100  POE-B 100 45 100  POE-C 100  PU/SEEPS 20 35 20 PU-SEEPS Compound A 50 50Properties of the molded article Hardness [Shore A] 89 85 92 88 90 90 78Non-tackiness ◯ ◯ ◯ ◯ ◯ Δ Δ Flexibility ⊚ ⊚ ⊚ ⊚ ⊚ X X Mechanicalproperties Yield strength [kgf/cm²] 47 42 80 48 60 37 21 Elongation atyield point [%] 150  100  100  125  150  33 33 Non-migration ◯ ◯ ◯ ◯ ◯ ◯◯ Adhesion strength of the laminate structure Impossible ImpossibleImpossible Impossible Impossible Redily Redily Adhesion strength[kgf/cm] to peel to peel to peel to peel to peel Peeled Peeled

Examples 8 and 9

[0251] The SEEPS-2, the PL and the PU/SEEPS were premixed in an amountshown in Table 3. The resulting mixture was molten at 140° C. undernitrogen with a kneading machine [“Labo Plastomill 20R200”, trade name,made by Toyo Seiki Seisaku-sho Ltd]. To the resulting melt, the PVC wasblended in an amount shown in Table 3. The resulting blend wasmelt-kneaded at a temperature of 140° C. and a mill rotation speed of 40rpm under nitrogen for 5 minutes to give a vinyl chloride polymercomposition.

[0252] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 3.

Comparative Example 5

[0253] The SEEPS-2 and the PL were premixed in an amount shown in Table3. The resulting mixture was molten at 140° C. under nitrogen with akneading machine [“Labo Plastomill 20R200”, trade name, made by ToyoSeiki Seisaku-sho Ltd]. To the resulting melt, the PVC was blended in anamount shown in Table 3. The resulting blend was melt-kneaded at atemperature of 140° C. and a mill rotation speed of 40 rpm undernitrogen for 5 minutes to give a vinyl chloride polymer composition.

[0254] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 3.

Example 10

[0255] The block copolymer composition A [PU-SEEPS Compound A] obtainedin the Referential Example 1, the SEEPS-2 and the PL were premixed in anamount shown in Table 3. The resulting mixture was molten at 140° C.under nitrogen with a kneading machine [“Labo Plastomill 20R200”, tradename, made by Toyo Seiki Seisaku-sho Ltd]. To the resulting melt, thePVC was blended in an amount shown in Table 3. The resulting blend wasmelt-kneaded at a temperature of 140° C. and a mill rotation speed of 40rpm under nitrogen for 5 minutes to give a vinyl chloride polymercomposition.

[0256] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 3. TABLE 3Comparative Examples Example 8 9 10 5 Composition [Part by weight] PVC100  100  100  100  SEEPS-2 33 50 33 50 PL 33 50 33 50 PU/SEEPS 17 50PU-SEEPS 17 Compound A Properties of the molded article Hardness [ShoreA] 82 71 81 71 Non-tackiness ◯ ◯ ◯ Δ Flexibility ⊚ ⊚ ⊚ X Mechanicalproperties Yield strength 37   32¹⁾ 38   18¹⁾ [kgf/cm²] Elongation atyield 150    200¹⁾  150    250¹⁾  point [%] Non-migration ◯ ◯ ◯ ◯Adhesion strength of Impossible Impossible Impossible Readily thelaminate structure to peel to peel to peel peeled Adhesion strength[kgf/cm]

Example 11

[0257] A high polymer polyol [POH-1] containing 15 ppm of dibutyltindiacetate [catalyst for polyurethane forming reaction], a chain extender[BD] and an organic diisocyanate [MDI] were fed into the feed zone of atwin-screw extruder [30 mm f, L/D=36; the heating zone is divided intothe feed zone, the compression zone and the metering zone] with coaxialscrews, wherein their molar ratio of POH-1:BD:MDI was 1.0:2.0:3.0[nitrogen atom content: 1.9% by weight] and their total feed rate was100 g/minutes, and continuously melt-polymerized at 260° C. to effect apolyurethane formation. A functionality block copolymer [F-SEEPS] wascontinuously fed into the compression zone of the twin-screw extruder ata feed rate of 100 g/minutes to effect the reaction with the resultingproduct of the above-described polyurethane formation. The resultingmelt was continuously extruded into water as a strand, and the resultingstrands were cut in pellets with a palletizing machine. The resultingpellets were dried at 80° C. for 4 hours to give the block copolymercomposition B [PU-SEEPS Compound B].

[0258] A part of the block copolymer composition B [PU-SEEPS Compound B]was sampled and the polyurethane contained therein was extracted therefrom with dimethyl formamide. Next, the SEEPS-1 and the unreactedSEEPS-OH were extracted from the sample with cyclohaxane. The remainingsolid was dried to give a block copolymer B. ¹H-NMR analysis showed thatthe block copolymer B was adi-block copolymer having one polymer block(I) comprising polystyrene block-hydrogenated copolymer block ofisoprene and butadiene-polystyrene block and one polymer block (II)comprising a polyurethane of poly(3-methyl-1,5-pentanediol adipate)unit, 4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit. Inaddition, GPC analysis showed that the extract by cyclohexane containeda tri-block copolymer having two polymer blocks (I) comprisingpolystyrene block-hydrogenated copolymer block of isoprene andbutadiene-polystyrene block and one polymer block (II) comprising apolyurethane of poly(3-methyl-1,5-pentanediol adipate) unit,4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit.

[0259] The amounts of the polyurethane, which was extracted withdimethylformamide, the SEEPS-OH, the SEEPS-1 and the tri-blockcopolymer, which were extracted with cyclohexane, were 183 parts byweight of the polyurethane, 0 part by weight of the SEEPS-OH, 22 partsby weight of the SEEPS-1 and 130 parts by weight of the tri-blockcopolymer, respectively, based on 100 parts by weight of the di-blockcopolymer.

[0260] Each of the polymer blocks (I) of the di-block copolymer and thetri-block copolymer had the same profiles as those of the SEEPS-1. Thenumber average molecular weight of the di-block copolymer was 85,000.Also, The number average molecular weight of the tri-block copolymer was102,000.

[0261] 100 parts by weight of the PVC and 100 parts by weight of theblock copolymer composition B [PU-SEEPS Compound B] were melt-kneadedwith a kneading machine [“Labo Plastomill 20R200”, trade name, made byToyo Seiki Seisaku-sho Ltd] at a temperature of 140° C. and a millrotation speed of 40 rpm under nitrogen for 5 minutes to give a vinylchloride polymer composition.

[0262] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 4.

Example 12

[0263] A high polymer polyol [POH-1] containing 15 ppm of dibutyltindiacetate [catalyst for polyurethane forming reaction], a chain extender[BD] and an organic diisocyanate [MDI] were fed into the feed zone of atwin-screw extruder [30 mm f, L/D=36; the heating zone is divided intothe feed zone, the compression zone and the metering zone] with coaxialscrews, wherein their molar ratio of POH-1:BD:MDI was 1.0:2.0:3.0[nitrogen atom content: 1.9% by weight] and their total feed rate was100 g/minutes, and continuously melt-polymerized at 260° C. to effect apolyurethane formation. A functionality block copolymer [F-HVSIS] wascontinuously fed into the compression zone of the twin-screw extruder ata feed rate of 100 g/minutes to effect the reaction with the resultingproduct of the above-described polyurethane formation. The resultingmelt was continuously extruded into water as a strand, and the resultingstrands were cut in pellets with a palletizing machine. The resultingpellets were dried at 80° C. for 4 hours to give the block copolymercomposition C [PU-HVSIS Compound C].

[0264] A part of the block copolymer composition C [PU-HVSIS Compound C]was sampled and the polyurethane contained therein was extractedtherefrom with dimethylformamide. Next, the HVSIS and the unreactedHVSIS-OH were extracted from the sample with cyclohaxane. The remainingsolid was dried to give a block copolymer C. ¹H-NMR analysis showed thatthe block copolymer C was a di-block copolymer having one polymer block(I) comprising polystyrene block-hydrogenated polyisopreneblock-polystyrene block and one polymer block (II) comprising apolyurethane of poly(3-methyl-1,5-pentanediol adipate) unit,4,4′-diphenylmethane diisocyanate unit and 1,4-butanediol unit. Inaddition, GPC analysis showed that the extract by cyclohexane containeda tri-block copolymer having two polymer blocks (I) comprisingpolystyrene block-hydrogenated polyisoprene block-polystyrene block andone polymer block (II) comprising a polyurethane ofpoly(3-methyl-1,5-pentanediol adipate) unit, 4,4′-diphenylmethanediisocyanate unit and 1,4-butanediol unit.

[0265] The amounts of the polyurethane, which was extracted withdimethylformamide, the HVSIS-OH, the HVSIS and the tri-block copolymer,which were extracted with cyclohexane, were 182 parts by weight of thepolyurethane, 0 part by weight of the HVSIS-OH, 45 parts by weight ofthe HVSIS and 127 parts by weight of the tri-block copolymer,respectively, based on 100 parts by weight of the di-block copolymer.

[0266] Each of the polymer blocks (I) of the di-block copolymer and thetri-block copolymer had the same profiles as those of the HVSIS. Thenumber average molecular weight of the di-block copolymer was 155,000.Also, The number average molecular weight of the tri-block copolymer was165,000.

[0267] 100 parts by weight of the PVC and 100 parts by weight of theblock copolymer composition C [PU-HVSIS Compound C] were melt-kneadedwith a kneading machine [“Labo Plastomill 20R200”, trade name, made byToyo Seiki Seisaku-sho Ltd] at a temperature of 140° C. and a millrotation speed of 40 rpm under nitrogen for 5 minutes to give a vinylchloride polymer composition.

[0268] By using the obtained vinyl chloride polymer composition, amolded article [test piece] and a laminate structure were prepared. Thenthe various properties of the molded article and the adhesion strengthin the laminate structure were measured and evaluated according to theabove-described methods. Results are shown in the Table 4. TABLE 4Examples 11 12 Composition [Part by weight] PVC 100 100 PU-SEEPSCompound B 100 PU-HVSIS Compound C 100 Properties of the molded articleHardness [Shore A]  93  93 Non-tackiness ◯ ◯ Flexibility ⊚ ⊚ Mechanicalproperties Yield strength [kgf/cm²]   123¹⁾  96 Elongation at yieldpoint [%]   150¹⁾ 180 Non-migration ◯ ◯ Adhesion strength of theImpossible Impossible laminate structure to peel to peel Adhesionstrength [kgf/cm]

[0269] From the results shown on the Tables 1 to 4, it is apparent thatthe vinyl chloride polymer composition of the present invention hasnon-tackiness and excellent handling properties. It can be alsounderstood that that the vinyl chloride polymer composition of thepresent invention can give a molded article having excellent mechanicalproperties and shows high adhesion strength to other materials.

Industrial applicability

[0270] The present provides a vinyl chloride polymer composition whichhas non-tackiness, excellent handling properties, favorable flexibilityand mechanical properties, and favorable melt-adhesiveness to othermaterials, and shows no migration of the component serving as aplasticizer.

[0271] The vinyl chloride polymer composition of the present inventioncan be applied for various uses such as a production of various moldedarticles and a production of a laminated structure with other materials.

1. A vinyl chloride polymer composition comprising (i) a vinyl chloridepolymer (a) and (ii) a block copolymer (b) having a polymer block (I) ofa block copolymer, which may be hydrogenated, of an aromatic vinylcompound polymer block and a conjugated diene polymer block, and apolymer block (II) of a polyurethane, in an amount such that the weightof the vinyl chloride polymer (a) and that of the block copolymer (b)satisfy the following equation (1): 30/70≦Wa/Wb≦98/2  (1); wherein Waand Wb mean the weights of the vinyl chloride polymer (a) and the blockcopolymer (b), respectively.
 2. The vinyl chloride polymer compositionaccording to claim 1, further comprising a thermoplastic polyurethane(c) in an amount of not more than 1000 parts by weight based on 100parts by weight of the block copolymer (b).
 3. The vinyl chloridepolymer composition according to claim 1 or 2, further comprising ablock copolymer (d), which may be hydrogenated, having an aromatic vinylcompound polymer block and a conjugated diene polymer block, in anamount of not more than 500 parts by weight based on 100 parts by weightof the block copolymer (b).
 4. The vinyl chloride polymer compositionaccording to any one of claims 1 to 3, further comprising anethylene-α-olefin copolymer (e), in an amount such that the weight ofthe ethylene-α-olefin copolymer (e) satisfies the following equations(2) and (3): 1/100≦Wb/(Wa+We)≦100/100  (2)30/70≦Wa/We≦95/5  (3); whereinWe means the weight of the ethylene-α-olefin copolymer (e).
 5. The vinylchloride polymer composition according to claim 3 or 4, furthercomprising a paraffin oil (f), in an amount such that the weights of theblock copolymer (d) and the paraffin oil (f) satisfy the followingequations (4) to (6):1/100≦Wb/(Wa+Wd+Wf)≦100/100  (4)25/75≦Wd/Wf≦95/5  (5)30/70≦Wa/(Wd+Wf)≦95/5  (6);wherein Wd and Wf mean the weights of the block copolymer (d) which maybe hydrogenated, having an aromatic vinyl compound polymer block and aconjugated diene polymer block and the paraffin oil (f), respectively.6. A molded article comprising the vinyl chloride polymer compositionaccording to any one of claims 1 to
 5. 7. A composite article comprisingthe vinyl chloride polymer composition according to any one of claims 1to 5 and another material.
 8. The composite article according to claim7, wherein another material is a material having a polarity.